Aqueous batteries,renowned for their cost-effectiveness and non-flammability,have attracted considerable attention in the realm of batteries featuring Zn-based and Sn-based configurations.These configurations employ Z...Aqueous batteries,renowned for their cost-effectiveness and non-flammability,have attracted considerable attention in the realm of batteries featuring Zn-based and Sn-based configurations.These configurations employ Zn and Sn metal anodes,respectively.While the growth patterns of Zn under various current densities have been extensively studied,there has been a scarcity of research on Sn dendrite growth.Our operando imaging analysis reveals that,unlike Zn,Sn forms sharp dendrites at high current density emphasizing the crucial necessity for implementing strategies to suppress the dendrites formation.To address this issue,we introduced a carbon nanotube(CNT)layer on copper foil,effectively preventing the formation of Sn dendrites under high current density,thus enabling the high-current operation of Sn metal batteries.We believe that our work highlights the importance of suppressing dendrite formation in aqueous Sn metal batteries operating at high current density and introduces a fresh perspective on mitigating Sn dendrite formation.展开更多
Rechargeable lithium–sulfur(Li–S)batteries are considered promising next-generation energy storage systems owing to their high theoretical energy density,but their application is hindered by the shuttle effect arisi...Rechargeable lithium–sulfur(Li–S)batteries are considered promising next-generation energy storage systems owing to their high theoretical energy density,but their application is hindered by the shuttle effect arising from dissolved lithium polysulfides(LiPSs).Herein,we design an optimized electrolyte to achieve long-term stability by employing an appropriate low-polarity solvent.A combination of diethyl ether(DEE)and 1,2-dimethoxyethane(DME)was selected to improve Li metal stability even in the presence of LiPSs.The DEE/DME electrolyte not only suppresses parasitic reactions between Li and LiPSs but also promotes uniform Li deposition.Moreover,operando optical microscopy was employed to directly visualize electrolyte stability and dendrite evolution in real time,while quantitative analysis was conducted via normalized hue index and contour image mapping.The enhanced anode stability of the DEE/DME electrolyte enabled excellent cycling performance,retaining 80.14%of its initial capacity after300 cycles at 3 C,while maintaining superior performance under practical conditions with high sulfur loading and a low E/S ratio.These findings highlight that solvent properties critically influence Li metal stabilization in Li–S batteries and underscore the significance of solvent engineering in electrolyte design.展开更多
The electrolyte additive,lithium nitrate(LiNO_(3)),is widely recognized for suppressing dendritic lithium growth in anode-free lithium metal batteries,yet its stabilizing effect is transient,and the mechanistic origin...The electrolyte additive,lithium nitrate(LiNO_(3)),is widely recognized for suppressing dendritic lithium growth in anode-free lithium metal batteries,yet its stabilizing effect is transient,and the mechanistic origin of this limitation has remained unresolved.Here,we uncover the origin of this behavior through a comprehensive analysis driven by artifact/damage-free direct cryogenic transmission electron microscopy,which enabled one of the most chemically specific and morphologically intuitive visualizations to date of intact solid-electrolyte interphases(SEIs)and lithium growth.Contrary to conventional interpretations centered on nitrogen-rich or single-component SEIs,we reveal that LiNO_(3) rapidly generates lithium hydroxide(LiOH)and lithium oxide(Li_(2)O)rich interphases,whose complementary functions—ionic transport through LiOH and mechanical robustness from Li_(2)O—synergistically suppress whisker nucleation and favor compact,particle-like growth.Over the extended plating,however,depletion of these species in combination with crystallographically favored orientations drives the particle-towhisker transition,explaining why the effectiveness of LiNO_(3) is inherently limited.This direct mechanistic visualization resolves a long-standing ambiguity regarding the transient efficacy of LiNO_(3) and reframes its function from a nitrogen-driven mechanism to a synergistic dual oxygen-interphase framework.Beyond mechanistic clarification,these findings establish that continuous regeneration of LiOH and Li_(2)O is essential for stable lithium deposition,offering a design principle for the development of durable electrolytes in high-performance anode-free lithium metal batteries.展开更多
Proton exchange membrane water electrolysis (PEMWE) requires Pt-based hydrogen evolution reaction (HER) electrocatalysts, which makes current systems costly. Low-cost alternatives have struggled to meet the requiremen...Proton exchange membrane water electrolysis (PEMWE) requires Pt-based hydrogen evolution reaction (HER) electrocatalysts, which makes current systems costly. Low-cost alternatives have struggled to meet the requirements of both electrocatalytic activity and durability at high-current density operations. Here, we developed phosphorus-modified nickel with ruthenium nanoclusters self-supported on carbon paper (P-NiRu/CP) as efficient HER electrocatalysts. By leveraging metal-organic framework precursors and optimizing the phosphidation process, a dynamic interface between Ru, Ni, and P exhibited optimized hydrogen adsorption/desorption energies and facilitated hydrogen mobility, promoting efficient Tafel recombination. The P-NiRu/CP exhibited an overpotential of 22 mV at 10 mA cm^(−2) and a Tafel slope of 29 mV dec^(−1), outperforming benchmark Pt/C. Computational studies revealed that the dynamic interface in P-NiRu/CP enhanced the electrocatalytic activity. When employed as the cathode in a PEMWE single cell (with commercial IrO2 as the anode) operating with pure deionized water, P-NiRu/CP achieved 2.05 V at 3.0 A cm^(−2) with stable operation over 500 h, highlighting P-NiRu/CP as a cost-effective, durable, and scalable electrocatalyst for sustainable hydrogen production.展开更多
Lithium–sulfur(Li–S)batteries are promising candidates for next-generation energy storage systems,but practical use is limited by polysulfide(PS)shuttling and Li metal anode instability.Lithium nitrate(LiNO_(3))is w...Lithium–sulfur(Li–S)batteries are promising candidates for next-generation energy storage systems,but practical use is limited by polysulfide(PS)shuttling and Li metal anode instability.Lithium nitrate(LiNO_(3))is widely used to mitigate these issues;however,its interfacial effects across the anode,electrolyte,and cathode during operation are not fully understood.Here,operando optical microscopy with a custom side-by-side cell enables simultaneous monitoring of the Li anode,liquid electrolyte,and sulfur cathode in a single field of view under conditions with and without LiNO_(3).In the absence of LiNO_(3),the Li surface undergoes rough stripping and fragmented,non-coalescent deposition,accompanied by PS-induced corrosion and accumulation of parasitic byproducts at the anode-electrolyte interface.Redness Intensity(RI),introduced to quantify electrolyte-phase PS dynamics,indicates sustained transport toward the anode and delayed conversion to elemental sulfur.By contrast,LiNO_(3)induces uniform Li stripping and the growth of aggregated,interconnected deposits,while mitigating PS crossover and promoting efficient sulfur crystallization at the cathode.Complementary SEM-EDS,UV–vis,XPS,TXM,and CT analyses corroborate these observations.By elucidating the multifunctional role of LiNO_(3),this study clarifies the interfacial dynamics that govern Li–S battery performance.展开更多
基金supported by the Institute for Basic Science,south korea(IBS-R006-A2)supproted by the Basic Science Research Program through the National Research Foundation of Korea(NRF),south korea funded by the Ministry of Education(2018R1D1A3B05042787)+1 种基金supported by the National Research Foundation of Korea(NRF),south korea grant funded by the Korea Government(MSIT)(RS-2025-00518953)the National Research Foundation of Korea(NRF),south korea grant funded by the Korea Government(MSIT)(RS-202400422387)。
文摘Aqueous batteries,renowned for their cost-effectiveness and non-flammability,have attracted considerable attention in the realm of batteries featuring Zn-based and Sn-based configurations.These configurations employ Zn and Sn metal anodes,respectively.While the growth patterns of Zn under various current densities have been extensively studied,there has been a scarcity of research on Sn dendrite growth.Our operando imaging analysis reveals that,unlike Zn,Sn forms sharp dendrites at high current density emphasizing the crucial necessity for implementing strategies to suppress the dendrites formation.To address this issue,we introduced a carbon nanotube(CNT)layer on copper foil,effectively preventing the formation of Sn dendrites under high current density,thus enabling the high-current operation of Sn metal batteries.We believe that our work highlights the importance of suppressing dendrite formation in aqueous Sn metal batteries operating at high current density and introduces a fresh perspective on mitigating Sn dendrite formation.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT)(RS-2024-00455177)the National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT)(RS-2025-00518953)+2 种基金the National Research Council of Science&Technology(NST)grant by the Korea government(MSIT)(GTL24012-000)the support by the National Natural Science Foundation of China(T2322015)the support by The Ministry of Science and ICT in Korea via KBSI(C524100)。
文摘Rechargeable lithium–sulfur(Li–S)batteries are considered promising next-generation energy storage systems owing to their high theoretical energy density,but their application is hindered by the shuttle effect arising from dissolved lithium polysulfides(LiPSs).Herein,we design an optimized electrolyte to achieve long-term stability by employing an appropriate low-polarity solvent.A combination of diethyl ether(DEE)and 1,2-dimethoxyethane(DME)was selected to improve Li metal stability even in the presence of LiPSs.The DEE/DME electrolyte not only suppresses parasitic reactions between Li and LiPSs but also promotes uniform Li deposition.Moreover,operando optical microscopy was employed to directly visualize electrolyte stability and dendrite evolution in real time,while quantitative analysis was conducted via normalized hue index and contour image mapping.The enhanced anode stability of the DEE/DME electrolyte enabled excellent cycling performance,retaining 80.14%of its initial capacity after300 cycles at 3 C,while maintaining superior performance under practical conditions with high sulfur loading and a low E/S ratio.These findings highlight that solvent properties critically influence Li metal stabilization in Li–S batteries and underscore the significance of solvent engineering in electrolyte design.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT)(No.RS-2024-00406724(50%)RS-2023-00222411,RS-2025-24533073)+2 种基金the Korea Basic Science Institute(National research Facilities and Equipment Center)grant funded by the Korea government(MOE)(RS-2024-00436346)the Korea Institute for Advancement of Technology(KIAT)grant funded by the Korea government(MOTIE)(RS-2024-00417730,HRD Program for Industrial Innovation)the research fund of Hanyang University(HY-202100000003295)。
文摘The electrolyte additive,lithium nitrate(LiNO_(3)),is widely recognized for suppressing dendritic lithium growth in anode-free lithium metal batteries,yet its stabilizing effect is transient,and the mechanistic origin of this limitation has remained unresolved.Here,we uncover the origin of this behavior through a comprehensive analysis driven by artifact/damage-free direct cryogenic transmission electron microscopy,which enabled one of the most chemically specific and morphologically intuitive visualizations to date of intact solid-electrolyte interphases(SEIs)and lithium growth.Contrary to conventional interpretations centered on nitrogen-rich or single-component SEIs,we reveal that LiNO_(3) rapidly generates lithium hydroxide(LiOH)and lithium oxide(Li_(2)O)rich interphases,whose complementary functions—ionic transport through LiOH and mechanical robustness from Li_(2)O—synergistically suppress whisker nucleation and favor compact,particle-like growth.Over the extended plating,however,depletion of these species in combination with crystallographically favored orientations drives the particle-towhisker transition,explaining why the effectiveness of LiNO_(3) is inherently limited.This direct mechanistic visualization resolves a long-standing ambiguity regarding the transient efficacy of LiNO_(3) and reframes its function from a nitrogen-driven mechanism to a synergistic dual oxygen-interphase framework.Beyond mechanistic clarification,these findings establish that continuous regeneration of LiOH and Li_(2)O is essential for stable lithium deposition,offering a design principle for the development of durable electrolytes in high-performance anode-free lithium metal batteries.
基金supported by the National R&D Program through the National Research Foundation of Korea(NRF),funded by the Ministry of Science and ICT,Republic of Korea(RS-2024-00409901 and RS-2025-02304646).
文摘Proton exchange membrane water electrolysis (PEMWE) requires Pt-based hydrogen evolution reaction (HER) electrocatalysts, which makes current systems costly. Low-cost alternatives have struggled to meet the requirements of both electrocatalytic activity and durability at high-current density operations. Here, we developed phosphorus-modified nickel with ruthenium nanoclusters self-supported on carbon paper (P-NiRu/CP) as efficient HER electrocatalysts. By leveraging metal-organic framework precursors and optimizing the phosphidation process, a dynamic interface between Ru, Ni, and P exhibited optimized hydrogen adsorption/desorption energies and facilitated hydrogen mobility, promoting efficient Tafel recombination. The P-NiRu/CP exhibited an overpotential of 22 mV at 10 mA cm^(−2) and a Tafel slope of 29 mV dec^(−1), outperforming benchmark Pt/C. Computational studies revealed that the dynamic interface in P-NiRu/CP enhanced the electrocatalytic activity. When employed as the cathode in a PEMWE single cell (with commercial IrO2 as the anode) operating with pure deionized water, P-NiRu/CP achieved 2.05 V at 3.0 A cm^(−2) with stable operation over 500 h, highlighting P-NiRu/CP as a cost-effective, durable, and scalable electrocatalyst for sustainable hydrogen production.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT)(RS-2024-00455177)the National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT)(RS-2025-00518953)+1 种基金the National Research Council of Science&Technology(NST)grant by the Korea government(MSIT)(No.GTL24012-000)This study was also supported by LG Energy Solution.Jong-Seong Bae acknowledges the support by the Ministry of Science and ICT in Korea via KBSI(Grant No.C524100).
文摘Lithium–sulfur(Li–S)batteries are promising candidates for next-generation energy storage systems,but practical use is limited by polysulfide(PS)shuttling and Li metal anode instability.Lithium nitrate(LiNO_(3))is widely used to mitigate these issues;however,its interfacial effects across the anode,electrolyte,and cathode during operation are not fully understood.Here,operando optical microscopy with a custom side-by-side cell enables simultaneous monitoring of the Li anode,liquid electrolyte,and sulfur cathode in a single field of view under conditions with and without LiNO_(3).In the absence of LiNO_(3),the Li surface undergoes rough stripping and fragmented,non-coalescent deposition,accompanied by PS-induced corrosion and accumulation of parasitic byproducts at the anode-electrolyte interface.Redness Intensity(RI),introduced to quantify electrolyte-phase PS dynamics,indicates sustained transport toward the anode and delayed conversion to elemental sulfur.By contrast,LiNO_(3)induces uniform Li stripping and the growth of aggregated,interconnected deposits,while mitigating PS crossover and promoting efficient sulfur crystallization at the cathode.Complementary SEM-EDS,UV–vis,XPS,TXM,and CT analyses corroborate these observations.By elucidating the multifunctional role of LiNO_(3),this study clarifies the interfacial dynamics that govern Li–S battery performance.
