Building a stable solid electrolyte interphase(SEI)has been regarded to be highly effective for mitigating the dendrite growth and parasitic side reactions of Zn anodes.Herein,a robust inorganic composite SEI layer is...Building a stable solid electrolyte interphase(SEI)has been regarded to be highly effective for mitigating the dendrite growth and parasitic side reactions of Zn anodes.Herein,a robust inorganic composite SEI layer is in situ constructed by introducing an organic cysteine additive to achieve long lifetime Zn metal batteries.The chemisorbed cysteine derivatives are electrochemically reduced to trigger a local alkaline environment for generating a gradient layered zinc hydroxide based multicomponent interphase.Such a unique interphase is of significant advantage as a corrosion inhibitor and Zn^(2+)modulator to enable reversible plating/stripping chemistry with a reduced desolvation energy barrier.Accordingly,the cells with a thin glass fiber separator(260μm)deliver a prolonged lifespan beyond 2000 h and enhanced Coulombic efficiency of 99.5%over 450 cycles.This work will rationally elaborate in situ construction of a desirable SEI by implanting reductive additives for dendrite-free Zn anodes.展开更多
High-energy-density Li-S batteries are subjected to serious sulfur deactivation and short cycle lifetime caused by undesirable polysulfide shuttle effect and frantic lithium dendrite formation.In this work,a controlla...High-energy-density Li-S batteries are subjected to serious sulfur deactivation and short cycle lifetime caused by undesirable polysulfide shuttle effect and frantic lithium dendrite formation.In this work,a controllable cage-confinement strategy to fabricate molybdenum carbide(MoC)nanoclusters as a high-efficient sulfiphilic and lithiophilic regulator to mitigate the formidable issues of Li-S batteries is demonstrated.The sub-2 nm MoC nanoclusters not only guarantee robust chemisorption and fast electrocatalytic conversion of polysulfides to enhance the sulfur electrochemistry,but also homogenize Li^(+) flux to suppress the lithium dendrite growth.As a consequence,the MoC-modified separator endows the batteries with boosted reaction kinetics,promoted sulfur utilization,and improved cycling stability.A reversible capacity of 701 mAh·g^(−1) at a high rate of 5.0C and a small decay rate of 0.076%per cycle at 1.0C over 600 cycles are achieved.This study offers a rational route for design and synthesis of bifunctional nanoclusers with both sulfiphilicity and lithiophilicity for high-performance Li-S batteries.展开更多
Hard carbon anode has shown extraordinary potentials for sodium-ion batteries(SIBs)owing to the cost-effectiveness and advantaged microstructure.Nevertheless,the widespread application of hard carbon is still hindered...Hard carbon anode has shown extraordinary potentials for sodium-ion batteries(SIBs)owing to the cost-effectiveness and advantaged microstructure.Nevertheless,the widespread application of hard carbon is still hindered by the insufficient sodium storage capacity and depressed rate property,which are mainly induced by the undesirable pseudographitic structure.Herein,we develop a molten-salt-mediated strategy to regulate the pseudographitic structure of hard carbon with suitable interlayer spacing and enlarged pseudographitic domain,which is conducive to the intercalation capacity and diffusion kinetics of sodium ions.Impressively,the optimized hard carbon anode delivers a high reversible capacity of 320 mAh·g^(−1),along with superior rate property(138 mAh·g−1 at 2 A·g^(−1))and stable cyclability over 1800 cycles.Moreover,the in situ Raman spectroscopic study and full-cell assembly further investigate the sodium storage mechanism and practical implement of obtained hard carbon.This work pioneers a low-cost and effective route to regulate the pseudographitic structure of hard carbon materials for advanced SIBs.展开更多
Rechargeable aqueous Zn/MnO_(2)batteries raise massive research activities in recent years. However, both the working principle and the degradation mechanism of this battery chemistry are still under debate. Herein, w...Rechargeable aqueous Zn/MnO_(2)batteries raise massive research activities in recent years. However, both the working principle and the degradation mechanism of this battery chemistry are still under debate. Herein, we provide an in-depth electrochemical and structural investigation on this controversial issue based on α-MnO_(2)crystalline nanowires. Mechanistic analysis substantiates a two-electron reaction pathway of Mn2+/Mn4+redox couple from part of MnO_(2)accompanying with a reversible precipitation/dissolution of flaky zinc sulfate hydroxide(ZSH) during the discharge/charge processes. The formation of the ZSH layer is double-edged, which passivates the deep dissolution of MnO_(2)upon discharging,but promotes the electrochemical deposition kinetics of active MnO_(2)upon charging. The cell degradation originates primarily from the corrosion failure of metallic zinc anode and the accumulation of irreversible ZnMn2O_(4)phases on the cathode. The addition of MnSO_(4)to the electrolyte could afford supplementary capacity contribution via electro-oxidation of Mn2+. However, a high MnSO_(4)concentration will expedite the cell failure by corroding the metallic zinc anodes. The present study will shed a fundamental insight on developing new strategies toward practically viable Zn/MnO_(2)batteries.展开更多
Water electrolysis has been considered as a sustainable way for producing renewable energy of hydrogen.However,this process requires a low-cost and high-efficient hydrogen evolution reaction(HER)catalyst to improve th...Water electrolysis has been considered as a sustainable way for producing renewable energy of hydrogen.However,this process requires a low-cost and high-efficient hydrogen evolution reaction(HER)catalyst to improve the overall reaction efficiency.Molybdenum(Mo)-based electrocatalysts are regarded as the promising candidates to replace the benchmark but expensive Ptbased HER catalysts,due to their high activity and stability in a wide pH range.In this review,we present a comprehensive and critical summary on the recent progress in the Mo-based electrodes for HER,including molybdenum alloys,molybdenum sulfides,molybdenum selenides,molybdenum carbides,molybdenum phosphides,molybdenum borides,molybdenum nitrides,and molybdenum oxides.Particular attention is mainly focused on the synthetic methods of Mo-based materials,the strategies for increasing the catalytic activity,and the relationship between structure/composition and electrocatalytic performance.Finally,the future development and perspectives of Mo-based electrocatalysts toward high HER performance are proposed.展开更多
The development of transition metal phosphides as potential anode materials of sodium-ion batteries has been substantially hindered by their sluggish kinetics and significant volume change during the sodiation/desodia...The development of transition metal phosphides as potential anode materials of sodium-ion batteries has been substantially hindered by their sluggish kinetics and significant volume change during the sodiation/desodiation process.In this work,we put forward a rational design strategy to construct a hollow-structured CoP@C com-posite to achieve ultrafast and durable sodium energy storage.The CoP@C composite with a well-defined hollow dodecahedron architecture has been synthesized via a stepwise treatment of carbonization and pohsphorization on ZIF-67.The unique hollow carbon framework not only provides high-speed electron/ion transportation pathways for CoP to enable fast sodiation kinetics,but also accom-modates large volume change to stabilize the electrode structure.As a consequence,the CoP@C composite could exhibit an ultra-high rate capability of 105 mAh·g^(-1)at a current density of 30 A·g^(-1),and a long-term cycling life-time.The present study will pave a fresh strategy for exploring advanced high-power anode materials for sodium ion batteries.展开更多
基金financially supported by the National Natural Foundation of China(Nos.52272239 and 51821091)the Fundamental Research Funds for the Central Universities(Nos.D5000210894 and 3102019JC005)the testing fund from the Analytical&Testing Center of Northwestern Polytechnical University。
文摘Building a stable solid electrolyte interphase(SEI)has been regarded to be highly effective for mitigating the dendrite growth and parasitic side reactions of Zn anodes.Herein,a robust inorganic composite SEI layer is in situ constructed by introducing an organic cysteine additive to achieve long lifetime Zn metal batteries.The chemisorbed cysteine derivatives are electrochemically reduced to trigger a local alkaline environment for generating a gradient layered zinc hydroxide based multicomponent interphase.Such a unique interphase is of significant advantage as a corrosion inhibitor and Zn^(2+)modulator to enable reversible plating/stripping chemistry with a reduced desolvation energy barrier.Accordingly,the cells with a thin glass fiber separator(260μm)deliver a prolonged lifespan beyond 2000 h and enhanced Coulombic efficiency of 99.5%over 450 cycles.This work will rationally elaborate in situ construction of a desirable SEI by implanting reductive additives for dendrite-free Zn anodes.
基金This study was financially supported by the research funds from the National Natural Science Foundation of China(No.52272239)the Fundamental Research Funds for the Central Universities(Nos.D5000210894 and 3102019JC005)the Analytical&Testing Center of Northwestern Polytechnical University for TEM analysis.
文摘High-energy-density Li-S batteries are subjected to serious sulfur deactivation and short cycle lifetime caused by undesirable polysulfide shuttle effect and frantic lithium dendrite formation.In this work,a controllable cage-confinement strategy to fabricate molybdenum carbide(MoC)nanoclusters as a high-efficient sulfiphilic and lithiophilic regulator to mitigate the formidable issues of Li-S batteries is demonstrated.The sub-2 nm MoC nanoclusters not only guarantee robust chemisorption and fast electrocatalytic conversion of polysulfides to enhance the sulfur electrochemistry,but also homogenize Li^(+) flux to suppress the lithium dendrite growth.As a consequence,the MoC-modified separator endows the batteries with boosted reaction kinetics,promoted sulfur utilization,and improved cycling stability.A reversible capacity of 701 mAh·g^(−1) at a high rate of 5.0C and a small decay rate of 0.076%per cycle at 1.0C over 600 cycles are achieved.This study offers a rational route for design and synthesis of bifunctional nanoclusers with both sulfiphilicity and lithiophilicity for high-performance Li-S batteries.
基金the National Natural Science Foundation of China(No.51772249)Key Research and Technological Achievements Transformation Plan Project of Inner Mongolia Autonomous Region(No.2023YFHH0063)Fundamental Research Funds for the Central Universities(No.3102019JC005).
文摘Hard carbon anode has shown extraordinary potentials for sodium-ion batteries(SIBs)owing to the cost-effectiveness and advantaged microstructure.Nevertheless,the widespread application of hard carbon is still hindered by the insufficient sodium storage capacity and depressed rate property,which are mainly induced by the undesirable pseudographitic structure.Herein,we develop a molten-salt-mediated strategy to regulate the pseudographitic structure of hard carbon with suitable interlayer spacing and enlarged pseudographitic domain,which is conducive to the intercalation capacity and diffusion kinetics of sodium ions.Impressively,the optimized hard carbon anode delivers a high reversible capacity of 320 mAh·g^(−1),along with superior rate property(138 mAh·g−1 at 2 A·g^(−1))and stable cyclability over 1800 cycles.Moreover,the in situ Raman spectroscopic study and full-cell assembly further investigate the sodium storage mechanism and practical implement of obtained hard carbon.This work pioneers a low-cost and effective route to regulate the pseudographitic structure of hard carbon materials for advanced SIBs.
基金the research fund of National Natural Science Foundation of China (No. 51821091)Fundamental Research Funds for the Central Universities (Nos.D5000210894 and 3102019JC005)。
文摘Rechargeable aqueous Zn/MnO_(2)batteries raise massive research activities in recent years. However, both the working principle and the degradation mechanism of this battery chemistry are still under debate. Herein, we provide an in-depth electrochemical and structural investigation on this controversial issue based on α-MnO_(2)crystalline nanowires. Mechanistic analysis substantiates a two-electron reaction pathway of Mn2+/Mn4+redox couple from part of MnO_(2)accompanying with a reversible precipitation/dissolution of flaky zinc sulfate hydroxide(ZSH) during the discharge/charge processes. The formation of the ZSH layer is double-edged, which passivates the deep dissolution of MnO_(2)upon discharging,but promotes the electrochemical deposition kinetics of active MnO_(2)upon charging. The cell degradation originates primarily from the corrosion failure of metallic zinc anode and the accumulation of irreversible ZnMn2O_(4)phases on the cathode. The addition of MnSO_(4)to the electrolyte could afford supplementary capacity contribution via electro-oxidation of Mn2+. However, a high MnSO_(4)concentration will expedite the cell failure by corroding the metallic zinc anodes. The present study will shed a fundamental insight on developing new strategies toward practically viable Zn/MnO_(2)batteries.
基金financially supported by the National Natural Science Foundation of China(Nos.51772249 and 51821091)the Fundamental Research Funds for the Central Universities(Nos.G2017KY0308 and 3102019JC005)+2 种基金the Natural Science Foundation of Shaanxi Province(Nos.2018JM5092 and 2019JLM-26)the Innovation Program for Talent(No.2019KJXX066)the Post-doctoral Program of Shaanxi Province(No.2018BSHTDZZ16)
文摘Water electrolysis has been considered as a sustainable way for producing renewable energy of hydrogen.However,this process requires a low-cost and high-efficient hydrogen evolution reaction(HER)catalyst to improve the overall reaction efficiency.Molybdenum(Mo)-based electrocatalysts are regarded as the promising candidates to replace the benchmark but expensive Ptbased HER catalysts,due to their high activity and stability in a wide pH range.In this review,we present a comprehensive and critical summary on the recent progress in the Mo-based electrodes for HER,including molybdenum alloys,molybdenum sulfides,molybdenum selenides,molybdenum carbides,molybdenum phosphides,molybdenum borides,molybdenum nitrides,and molybdenum oxides.Particular attention is mainly focused on the synthetic methods of Mo-based materials,the strategies for increasing the catalytic activity,and the relationship between structure/composition and electrocatalytic performance.Finally,the future development and perspectives of Mo-based electrocatalysts toward high HER performance are proposed.
基金financially supported by the Innovation Foundation for National Natural Science Foundation of China (Nos.51772249 and 51821091)the Doctor Dissertation of Northwestern Polytechnical University (No.CX202025)the Fundamental Research Funds for the Central Universities (Nos. D5000210894 and 3102019JC005)
文摘The development of transition metal phosphides as potential anode materials of sodium-ion batteries has been substantially hindered by their sluggish kinetics and significant volume change during the sodiation/desodiation process.In this work,we put forward a rational design strategy to construct a hollow-structured CoP@C com-posite to achieve ultrafast and durable sodium energy storage.The CoP@C composite with a well-defined hollow dodecahedron architecture has been synthesized via a stepwise treatment of carbonization and pohsphorization on ZIF-67.The unique hollow carbon framework not only provides high-speed electron/ion transportation pathways for CoP to enable fast sodiation kinetics,but also accom-modates large volume change to stabilize the electrode structure.As a consequence,the CoP@C composite could exhibit an ultra-high rate capability of 105 mAh·g^(-1)at a current density of 30 A·g^(-1),and a long-term cycling life-time.The present study will pave a fresh strategy for exploring advanced high-power anode materials for sodium ion batteries.
