Heterogeneous structure and carbon coating are important ways to enhance the reaction kinetics and cycling stability of metal phosphides as anode materials for sodium-ion batteries.Therefore,nitrogen-doped carbon-capp...Heterogeneous structure and carbon coating are important ways to enhance the reaction kinetics and cycling stability of metal phosphides as anode materials for sodium-ion batteries.Therefore,nitrogen-doped carbon-capped triphasic heterostructure Cu_(3)P/Co_(2)P/CoP@NC stands for nitrogen doped carbon nanorods were designed and synthesized through a combination of phosphide and carbonization.Kinetic analyses(cyclic voltammetry,electrochemical impedance spectroscopy,and galvanostatic intermittent titration technique)and density functional theory calculations show that the three-phase heterostructure and carbon layer effectively improve Na adsorption and migration as well as the electrochemical reactivity of the electrode.Based on this,Cu_(3)P/Co_(2)P/CoP@NC demonstrated excellent rate performance(305.9 mAh g^(-1)at 0.3 A g^(-1)and 202.8 mAh g^(-1)even at 10 A g^(-1))and cycling stability(the capacity decay rate is only 0.12%from the 5th to 300th cycle)when it is used for sodium-ion battery anodes.The in situ X-ray diffraction,ex situ X-ray photoelectron spectroscopy,and high-resolution transmission electron microscopy tests showed that Cu_(3)P/Co_(2)P/CoP@NC is based on a conversion reaction mechanism for sodium-ion storage.In addition,the NVP@reduced graphene oxide(rGO)//Cu_(3)P/Co_(2)P/CoP@NC full-cell delivers a high capacity of 210.2 mAh g^(-1)after 50 cycles at 0.3 A g^(-1).This work can provide a reference for the design of high-performance sodium electrode anode materials.展开更多
Aqueous zinc-ion batteries (AZIBs) are promising contenders for large-scale energy storage with the merits of their low cost,high safety,environmental friendliness,and competitive gravimetric energy density.Neverthele...Aqueous zinc-ion batteries (AZIBs) are promising contenders for large-scale energy storage with the merits of their low cost,high safety,environmental friendliness,and competitive gravimetric energy density.Nevertheless,suitable cathode materials with long cycle life and adequate capacity are still rare.Herein,we report a nanoflower vanadium tetrasulfide/carbon nanotubes (VS_(4)/CNTs) cathode with high Znstorage performance.We propose a phase transition reaction mechanism from VS_(4)to zinc pyrovanadate in the initial cycles and a reversible intercalation mechanism for Zn^(2+) in zinc pyrovanadate during subsequent cycles.As a result,the cathode delivers a high discharge capacity of 265 mAh g^(-1)at 0.25 A g^(-1)and 182 m Ah g^(-1)at 7 A g^(-1).In addition,the cathode exhibits a long-term cyclability with 93%capacity retention over 1200 cycles at 5 A g^(-1).VS_(4)/CNTs with superior electrochemical performance is a hopeful cathode material in AZIBs.展开更多
Garnet-structured ceramic electrolyte Li_(6.75)La_(3)Zr_(1.75)Ta_(0.25)O_(12)(LLZTO)attracts significant consideration in solid-state Li metal batteries due to its wide electrochemical window and favorable compatibili...Garnet-structured ceramic electrolyte Li_(6.75)La_(3)Zr_(1.75)Ta_(0.25)O_(12)(LLZTO)attracts significant consideration in solid-state Li metal batteries due to its wide electrochemical window and favorable compatibility with Li metal.However,the deployment of LLZTO is severely hampered by poor contact between LLZTO and Li metal anode.In this paper,an ultra-thin Al-Si interface buffer layer(10 nm)is constructed on LLZTO by a magnetron sputtering method,which allows superior wetting of Li onto the LLZTO surface due to the alloying reaction between the Al-Si layer and Li metal.The resulting Li/Al-Si coated LLZTO(ASL)/Li symmetrical cell delivers an interfacial resistance of 15.0Ωcm^(-2),which is much lower than that of 1140.3Ωcm^(-2)for the bare LLZTO symmetrical cell.Moreover,the Li/ASL/Li symmetrical cells exhibit stable plating/striping performance(800 h)with small voltage hysteresis at 1.0 mA cm^(-2).Besides,the full cell with LiFePO_(4)cathode reveals a high capacity of 124.1 mA h g^(-1)after 600 cycles at 0.5C with a lowcapacity decay of 0.032%per cycle.We believe this work will facilitate the development of solid-state rechargeable batteries.展开更多
The intrinsically safe Zn||I_(2) battery,one of the leading candidates aiming to replace traditional Pb-acid batteries,is still seriously suffering from short shelf and cycling lifespan,due to the uncontrolled I_(3)^(...The intrinsically safe Zn||I_(2) battery,one of the leading candidates aiming to replace traditional Pb-acid batteries,is still seriously suffering from short shelf and cycling lifespan,due to the uncontrolled I_(3)^(−)-shuttling and dynamic parasitic reactions on Zn anodes.Considering the fact that almost all these detrimental processes terminate on the surfaces of Zn anodes,modifying Zn anodes’surface with protecting layers should be one of the most straightforward and thorough approaches to restrain these processes.Herein,a facile zeolite-based cation-exchange protecting layer is designed to comprehensively suppress the unfavored parasitic reactions on the Zn anodes.The negatively-charged cavities in the zeolite lattice provide highly accessible migration channels for Zn^(2+),while blocking anions and electrolyte from passing through.This low-cost cation-exchange protecting layer can simultaneously suppress self-discharge,anode corrosion/passivation,and Zn dendrite growth,awarding the Zn||I_(2) batteries with ultra-long cycle life(91.92%capacity retention after 5600 cycles at 2 A g^(−1)),high coulombic efficiencies(99.76%in average)and large capacity(203–196 mAh g^(−1) at 0.2 A g^(−1)).This work provides a highly affordable approach for the construction of high-performance Zn-I_(2) aqueous batteries.展开更多
Aqueous zinc metal batteries(ZMBs)are one of the most promising grid-scale renewable energy storage batteries.However,the practical application of ZMBs is limited by uncontrollable Zn dendrites and parasitic side reac...Aqueous zinc metal batteries(ZMBs)are one of the most promising grid-scale renewable energy storage batteries.However,the practical application of ZMBs is limited by uncontrollable Zn dendrites and parasitic side reactions at the anode interface.Herein,a unique water-confinement hydrogel electrolyte(TONFC/PAM)was constructed by carboxyl-rich nanocellulose(TONFC)and acid amide-rich polyacrylamide(PAM).The parasitic side reactions were effectively suppressed due to limiting the movement of water in the designed hydrogel electrolyte.Meanwhile,the electrostatic interactions with the electron-rich group(-COOH and-CONH2)established fast Zn2+ion transport channels in the electrolyte,enabling an excellent ionic conductivity(30.23 mS cm^(-1))and horizontal deposition of Zn metal.As a result,the Zn||Zn cells and Zn||Cu cells with TONFC/PAM electrolyte achieve a long cycling life of over 1,400 h at 1 mA cm^(-2)and a high average coulombic efficiency of 99.4%,respectively.More importantly,the Zn||MnO2full cells can stably run for 1,000 cycles with a high capacity(~150 mAh g^(-1))at a current density of 2 A g^(-1).These results show that TONFC/PAM is a suitable hydrogel electrolyte for ZMBs,which presents attractive opportunities for future research on ZMBs.展开更多
Herein,the core-shell structured N-doped carbon coated Fe7S8 nano-aggregates(Fe7S8@NC)were controllably prepared via a simple three-step synthesis strategy.The appropriate thickness of N-doped carbon layer outside Fe7...Herein,the core-shell structured N-doped carbon coated Fe7S8 nano-aggregates(Fe7S8@NC)were controllably prepared via a simple three-step synthesis strategy.The appropriate thickness of N-doped carbon layer outside Fe7S8 nano-aggregates can not only inhibit the particle pulverization induced by the big volume changes of Fe7S8,but can increase the electron transfer efficiency.The hierarchical Fe7S8 nano-aggregates composed of some primary nanoparticles can accelerate the lithium or sodium diffusion kinetics.As anode materials for Li-ion batteries(LIBs),the well-designed Fe7S8@NC nanocomposites exhibit outstanding lithium storage performance,which is better than that of pure Fe7S8,Fe3O4@NC and Fe7S8@C.Among these nanocomposites,the N-doped carbon coated Fe7S8 with carbon content of 26.87 wt.%shows a high reversible specific capacity of 833 mAh·g^−1 after 1,000 cycles at a high current density of 2 A·g^−1.The above electrode also shows excellent high rate sodium storage performance.The experimental and theoretical analyses indicate that the outstanding electrochemical performance could be attributed to the synergistic effect of hierarchical Fe7S8 nanostructure and conductive N-doped carbon layer.The quantitative kinetic analysis indicates that the charge storage of Fe7S8@NC electrode is a combination of diffusion-controlled battery behavior and surface-induced capacitance behavior.展开更多
Cu(I)-catalyzed azide-alkyne cycloadditions(CuAAC)have gained increasing interest in the selective labeling of living cells and organisms with biomolecules.However,their application is constrained either by the high c...Cu(I)-catalyzed azide-alkyne cycloadditions(CuAAC)have gained increasing interest in the selective labeling of living cells and organisms with biomolecules.However,their application is constrained either by the high cytotoxicity of Cu(I)ions or the low activity of CuAAC in the internal space of living cells.This paper reports the design of a novel Cu-based nanocatalyst,watersoluble thiolated Cu30 nanoclusters(NCs),for living cell labeling via CuAAC.The Cu30 NCs offer good biocompatibility,excellent stability,and scalable synthesis(e.g.,gram scale),which would facilitate potential commercial applications.By combining the highly localized Cu(I)active species on the NC surface and good structural stability,the Cu30 NCs exhibit superior catalytic activities for a series of Huisgen cycloaddition reactions with good recyclability.More importantly,the biocompatibility of the Cu30 NCs enables them to be a good catalyst for CuAAC,whereby the challenging labeling of living cells can be achieved via CuAAC on the cell membrane.This study sheds light on the facile synthesis of atomically precise Cu NCs,as well as the design of novel Cu NCs-based nanocatalysts for CuAAC in intracellular bioorthogonal applications.展开更多
The electrochromic(EC)mechanisms of inorganic materials are usually based on reversible cation insertion/extraction or metal deposition/dissolution,which are plagued by ion trapping and dendrite growth,respectively.In...The electrochromic(EC)mechanisms of inorganic materials are usually based on reversible cation insertion/extraction or metal deposition/dissolution,which are plagued by ion trapping and dendrite growth,respectively.In this paper,a novel conversion-type electrochromic mechanism is proposed,by making good use of the CuI/Cu redox couple.This CuI-based electrochromic system shows a neutral color switching from transparent and dim grey.By simply increasing the bleaching voltage,I_(3)^(-)/I^(-)redox couple can be further activated.The generated I_(3)^(-)will readily react with Cu,effectively improving the conversion reversibility and thereby rejuvenating the degraded electrochromic performance.Thanks to the well-designed electrode and the self-healing ability,this conversion electrochromic system achieves rapid response times(tcoloring:23 s,tbleaching:6 s),decant optical modulation amplitude(26.4%),high coloration efficiency(86.15 cm^(2)·C^(-1)),admirable cyclic durability(without performance degradation after 480 cycles)and excellent optical memory ability(transmittance variation<1%after 10 h open-circuit storage).The establishment of this conversion-type electrochromism may inspire the exploration of novel electrochromic materials and devices.展开更多
基金supported by the National Natural Science Foundation of China (No. 22305210, 52371238 to C. D.)the Shandong Provincial Natural Science Foundation (No. ZR2020QB108)+1 种基金the Graduate Innovation Foundation of Yantai University (GIFYTU)the Shandong Laboratory of Advanced Materials and Green Manufacturing (Yantai, AMGM2024A01)
文摘Heterogeneous structure and carbon coating are important ways to enhance the reaction kinetics and cycling stability of metal phosphides as anode materials for sodium-ion batteries.Therefore,nitrogen-doped carbon-capped triphasic heterostructure Cu_(3)P/Co_(2)P/CoP@NC stands for nitrogen doped carbon nanorods were designed and synthesized through a combination of phosphide and carbonization.Kinetic analyses(cyclic voltammetry,electrochemical impedance spectroscopy,and galvanostatic intermittent titration technique)and density functional theory calculations show that the three-phase heterostructure and carbon layer effectively improve Na adsorption and migration as well as the electrochemical reactivity of the electrode.Based on this,Cu_(3)P/Co_(2)P/CoP@NC demonstrated excellent rate performance(305.9 mAh g^(-1)at 0.3 A g^(-1)and 202.8 mAh g^(-1)even at 10 A g^(-1))and cycling stability(the capacity decay rate is only 0.12%from the 5th to 300th cycle)when it is used for sodium-ion battery anodes.The in situ X-ray diffraction,ex situ X-ray photoelectron spectroscopy,and high-resolution transmission electron microscopy tests showed that Cu_(3)P/Co_(2)P/CoP@NC is based on a conversion reaction mechanism for sodium-ion storage.In addition,the NVP@reduced graphene oxide(rGO)//Cu_(3)P/Co_(2)P/CoP@NC full-cell delivers a high capacity of 210.2 mAh g^(-1)after 50 cycles at 0.3 A g^(-1).This work can provide a reference for the design of high-performance sodium electrode anode materials.
基金supported by the National Natural Science Foundation of China (51772257 and 52072328)the Basic Scientific Fund for National Public Research Institutes of China (2019Y03 and 2020S02)。
文摘Aqueous zinc-ion batteries (AZIBs) are promising contenders for large-scale energy storage with the merits of their low cost,high safety,environmental friendliness,and competitive gravimetric energy density.Nevertheless,suitable cathode materials with long cycle life and adequate capacity are still rare.Herein,we report a nanoflower vanadium tetrasulfide/carbon nanotubes (VS_(4)/CNTs) cathode with high Znstorage performance.We propose a phase transition reaction mechanism from VS_(4)to zinc pyrovanadate in the initial cycles and a reversible intercalation mechanism for Zn^(2+) in zinc pyrovanadate during subsequent cycles.As a result,the cathode delivers a high discharge capacity of 265 mAh g^(-1)at 0.25 A g^(-1)and 182 m Ah g^(-1)at 7 A g^(-1).In addition,the cathode exhibits a long-term cyclability with 93%capacity retention over 1200 cycles at 5 A g^(-1).VS_(4)/CNTs with superior electrochemical performance is a hopeful cathode material in AZIBs.
基金supported by the National Natural Science Foundation of China(22209140,52072328,and 52175192)the Incubation Program of Youth Innovation in Shandong Province and Natural Science Foundation of Shandong Province(ZR2022QE059)。
文摘Garnet-structured ceramic electrolyte Li_(6.75)La_(3)Zr_(1.75)Ta_(0.25)O_(12)(LLZTO)attracts significant consideration in solid-state Li metal batteries due to its wide electrochemical window and favorable compatibility with Li metal.However,the deployment of LLZTO is severely hampered by poor contact between LLZTO and Li metal anode.In this paper,an ultra-thin Al-Si interface buffer layer(10 nm)is constructed on LLZTO by a magnetron sputtering method,which allows superior wetting of Li onto the LLZTO surface due to the alloying reaction between the Al-Si layer and Li metal.The resulting Li/Al-Si coated LLZTO(ASL)/Li symmetrical cell delivers an interfacial resistance of 15.0Ωcm^(-2),which is much lower than that of 1140.3Ωcm^(-2)for the bare LLZTO symmetrical cell.Moreover,the Li/ASL/Li symmetrical cells exhibit stable plating/striping performance(800 h)with small voltage hysteresis at 1.0 mA cm^(-2).Besides,the full cell with LiFePO_(4)cathode reveals a high capacity of 124.1 mA h g^(-1)after 600 cycles at 0.5C with a lowcapacity decay of 0.032%per cycle.We believe this work will facilitate the development of solid-state rechargeable batteries.
基金The authors thank the National Natural Science Foundation of China(51502194,22133005,21973107,and 22103093)the Natural Science Foundation of Shandong(ZR2020ME024)+2 种基金the Science and Technology Commission of Shanghai Municipality(21ZR1472900)the Key Laboratory for Palygorskite Science and Applied Technology of Jiangsu Province(HPK202103)for financial supportOpen access funding provided by Shanghai Jiao Tong University
文摘The intrinsically safe Zn||I_(2) battery,one of the leading candidates aiming to replace traditional Pb-acid batteries,is still seriously suffering from short shelf and cycling lifespan,due to the uncontrolled I_(3)^(−)-shuttling and dynamic parasitic reactions on Zn anodes.Considering the fact that almost all these detrimental processes terminate on the surfaces of Zn anodes,modifying Zn anodes’surface with protecting layers should be one of the most straightforward and thorough approaches to restrain these processes.Herein,a facile zeolite-based cation-exchange protecting layer is designed to comprehensively suppress the unfavored parasitic reactions on the Zn anodes.The negatively-charged cavities in the zeolite lattice provide highly accessible migration channels for Zn^(2+),while blocking anions and electrolyte from passing through.This low-cost cation-exchange protecting layer can simultaneously suppress self-discharge,anode corrosion/passivation,and Zn dendrite growth,awarding the Zn||I_(2) batteries with ultra-long cycle life(91.92%capacity retention after 5600 cycles at 2 A g^(−1)),high coulombic efficiencies(99.76%in average)and large capacity(203–196 mAh g^(−1) at 0.2 A g^(−1)).This work provides a highly affordable approach for the construction of high-performance Zn-I_(2) aqueous batteries.
基金supported by the National Natural Science Foundation of China(22209140,52202286)the Natural Science Foundation of Shandong Province(ZR2022QE059)+5 种基金the Shandong Laboratory of Advanced Materials and Green Manufacturing at Yantai(AMGM2023A08)the Natural Science Foundation of Zhejiang Province(LQ23B030011,LY24B030006)the Scientific Research Fund of Zhejiang Provincial Education Department(Y202148249)Science and Technology Plan Project of Wenzhou Municipality(ZG2024055)Wenzhou Association for Science and Technology Innovation Program(NLTS2024-013)the Basic Research Project of Wenzhou City(G20220016)。
文摘Aqueous zinc metal batteries(ZMBs)are one of the most promising grid-scale renewable energy storage batteries.However,the practical application of ZMBs is limited by uncontrollable Zn dendrites and parasitic side reactions at the anode interface.Herein,a unique water-confinement hydrogel electrolyte(TONFC/PAM)was constructed by carboxyl-rich nanocellulose(TONFC)and acid amide-rich polyacrylamide(PAM).The parasitic side reactions were effectively suppressed due to limiting the movement of water in the designed hydrogel electrolyte.Meanwhile,the electrostatic interactions with the electron-rich group(-COOH and-CONH2)established fast Zn2+ion transport channels in the electrolyte,enabling an excellent ionic conductivity(30.23 mS cm^(-1))and horizontal deposition of Zn metal.As a result,the Zn||Zn cells and Zn||Cu cells with TONFC/PAM electrolyte achieve a long cycling life of over 1,400 h at 1 mA cm^(-2)and a high average coulombic efficiency of 99.4%,respectively.More importantly,the Zn||MnO2full cells can stably run for 1,000 cycles with a high capacity(~150 mAh g^(-1))at a current density of 2 A g^(-1).These results show that TONFC/PAM is a suitable hydrogel electrolyte for ZMBs,which presents attractive opportunities for future research on ZMBs.
基金the National Natural Science Foundation of China(No.51772257)the Major Basic Research Project of Shandong Natural Science Foundation(No.ZR2018ZC1459)Doctor Foundation of Shandong Province(No.ZR2017BB081)for financial support.
文摘Herein,the core-shell structured N-doped carbon coated Fe7S8 nano-aggregates(Fe7S8@NC)were controllably prepared via a simple three-step synthesis strategy.The appropriate thickness of N-doped carbon layer outside Fe7S8 nano-aggregates can not only inhibit the particle pulverization induced by the big volume changes of Fe7S8,but can increase the electron transfer efficiency.The hierarchical Fe7S8 nano-aggregates composed of some primary nanoparticles can accelerate the lithium or sodium diffusion kinetics.As anode materials for Li-ion batteries(LIBs),the well-designed Fe7S8@NC nanocomposites exhibit outstanding lithium storage performance,which is better than that of pure Fe7S8,Fe3O4@NC and Fe7S8@C.Among these nanocomposites,the N-doped carbon coated Fe7S8 with carbon content of 26.87 wt.%shows a high reversible specific capacity of 833 mAh·g^−1 after 1,000 cycles at a high current density of 2 A·g^−1.The above electrode also shows excellent high rate sodium storage performance.The experimental and theoretical analyses indicate that the outstanding electrochemical performance could be attributed to the synergistic effect of hierarchical Fe7S8 nanostructure and conductive N-doped carbon layer.The quantitative kinetic analysis indicates that the charge storage of Fe7S8@NC electrode is a combination of diffusion-controlled battery behavior and surface-induced capacitance behavior.
基金This work was supported by the National Natural Science Foundation of China(No.22071127)Taishan Scholar Foundation(No.tsqn201812074)+1 种基金the Natural Science Foundation of Shandong Province(No.ZR2019YQ07)the NanoBio Lab(IMRE,A*STAR,Singapore).
文摘Cu(I)-catalyzed azide-alkyne cycloadditions(CuAAC)have gained increasing interest in the selective labeling of living cells and organisms with biomolecules.However,their application is constrained either by the high cytotoxicity of Cu(I)ions or the low activity of CuAAC in the internal space of living cells.This paper reports the design of a novel Cu-based nanocatalyst,watersoluble thiolated Cu30 nanoclusters(NCs),for living cell labeling via CuAAC.The Cu30 NCs offer good biocompatibility,excellent stability,and scalable synthesis(e.g.,gram scale),which would facilitate potential commercial applications.By combining the highly localized Cu(I)active species on the NC surface and good structural stability,the Cu30 NCs exhibit superior catalytic activities for a series of Huisgen cycloaddition reactions with good recyclability.More importantly,the biocompatibility of the Cu30 NCs enables them to be a good catalyst for CuAAC,whereby the challenging labeling of living cells can be achieved via CuAAC on the cell membrane.This study sheds light on the facile synthesis of atomically precise Cu NCs,as well as the design of novel Cu NCs-based nanocatalysts for CuAAC in intracellular bioorthogonal applications.
基金the National Natural Science Foundation of China(Nos.52371238,22273081,52207249)the Natural Science Foundation of Shandong Province(No.ZR2020ME024)+1 种基金Taishan Young Scholar Program(No.tsqn202211114)the Open Foundation of Key Laboratory for Palygorskite Science and Applied Technology of Jiangsu Province(No.HPK202103)for financial support.
文摘The electrochromic(EC)mechanisms of inorganic materials are usually based on reversible cation insertion/extraction or metal deposition/dissolution,which are plagued by ion trapping and dendrite growth,respectively.In this paper,a novel conversion-type electrochromic mechanism is proposed,by making good use of the CuI/Cu redox couple.This CuI-based electrochromic system shows a neutral color switching from transparent and dim grey.By simply increasing the bleaching voltage,I_(3)^(-)/I^(-)redox couple can be further activated.The generated I_(3)^(-)will readily react with Cu,effectively improving the conversion reversibility and thereby rejuvenating the degraded electrochromic performance.Thanks to the well-designed electrode and the self-healing ability,this conversion electrochromic system achieves rapid response times(tcoloring:23 s,tbleaching:6 s),decant optical modulation amplitude(26.4%),high coloration efficiency(86.15 cm^(2)·C^(-1)),admirable cyclic durability(without performance degradation after 480 cycles)and excellent optical memory ability(transmittance variation<1%after 10 h open-circuit storage).The establishment of this conversion-type electrochromism may inspire the exploration of novel electrochromic materials and devices.
