Solid electrolyte interphase(SEI)is widely acknowledged as the most crucial and least comprehended component in secondary batteries.Particularly,fluorinated SEI derived from the decomposition of fluorinated salt/solve...Solid electrolyte interphase(SEI)is widely acknowledged as the most crucial and least comprehended component in secondary batteries.Particularly,fluorinated SEI derived from the decomposition of fluorinated salt/solvent electrolyte or additive has been widely applied to extend the lifespan of Li/Na anodes,and a similar strategy is being implemented for Zn metal electrodes.However,fluorine-containing electrolytes raise concerns regarding cost,toxicity,corrosivity,and environmental contamination.Moreover,the necessity and role of fluorine in the SEI component remain unclear,particularly in the aqueous system.Here,we report a fluorine-free inorganic-rich SEI layer in situ built by introducing a low-cost,low-concentration tetraethyl ammonium iodide(TEAI)into dilute aqueous ZnSO_(4)electrolyte.The TEAI additive is found to simultaneously modulate the Zn^(2+)solvation structure and optimize the chemisorption at the anode/electrolyte interface.The synergistic interaction between the I-/SO_(4)^(2-)anion-involved solvation structure and adsorbed TEA^(+)cations drives the formation of fluorine-free SEI with inorganics(Zn_(3)N_(2),Zn(IO_(3))_(2),Zn S,etc.),which are capable of providing fast Zn^(2+)transport ability,high-flux nucleation site,and preferential Zn(002)deposition.Besides the reductive decomposition with the formation of Irich SEI layer,the redox-active iodine species can rejuvenate inactive byproducts and dead Zn,allowing the interface self-healing and ensuring long-term interfacial stability.The TEAI-formulated electrolyte endows the Zn anode with excellent Zn reversibility by achieving dendrite-free Zn plating/stripping over 6500 h in the Zn||Zn symmetric battery at 1 mA cm^(-2).This study provides new insights into stabilizing Zn metal electrodes via robust fluorine-free interphases.展开更多
Despite its high capacity behavior as the anode for lithium-ion batteries (LIBs), SnO_(2) suffers the poorelectronic conductivity and high volume expansion, which lead to poor cycling stability and rate capability. In...Despite its high capacity behavior as the anode for lithium-ion batteries (LIBs), SnO_(2) suffers the poorelectronic conductivity and high volume expansion, which lead to poor cycling stability and rate capability. In this study, we employ defect engineering to design SnO_(2−x)(x = 0, 0.12, 0.2, and 0.3) nanoparticleswith varied oxygen vacancies. Notably, the SnO1.80 electrode with 20 % oxygen vacancies exhibits excellent electrochemical performance. Advanced physical characterizations combined with density functionaltheory (DFT) simulations demonstrate that the improved electrochemical performance can be attributedto the formation of a stable, uniform, and LiF-rich solid-electrolyte interface (SEI) layer through the optimization of oxygen vacancies. This study shows novel insights into the application of defect engineeringwithin oxides for the rational design of the uniform surface layer toward high-energy-density LIBs.展开更多
Aqueous zinc-ion batteries encounter impediments on their trajectory towards commercialization,primarily due to challenges such as dendritic growth,hydrogen evolution reaction.Throughout recent decades of investigatio...Aqueous zinc-ion batteries encounter impediments on their trajectory towards commercialization,primarily due to challenges such as dendritic growth,hydrogen evolution reaction.Throughout recent decades of investigation,electrolyte modulation by using function additives is widely considered as a facile and efficient way to prolong the Zn anode lifespan.Herein,N-(2-hydroxypropyl)ethylenediamine is employed as an additive to attach onto the Zn surface with a substantial adsorption energy with(002)facet.The as-formed in-situ solid-electrolyte interphase layer effectively mitigates hydrogen evolution reaction by constructing a lean-water internal Helmholtz layer.Additionally,N-(2-hydroxypropyl)ethylenediamine establishes a coordination complex with Zn^(2+),thereby modulating the solvation structure and enhancing the mobility of Zn^(2+).As expected,the Zn-symmetrical cell with N-(2-hydroxypropyl)ethylenediamine additive demonstrated successful cycling exceeding 1500 h under 1 mA cm^(-2) for0.5 mAh cm^(-2).Furthermore,the Zn//δ-MnO_(2) battery maintains a capacity of approximately 130 mAh g^(-1) after 800 cycles at 1 A g^(-1),with a Coulombic efficiency surpassing 98%.This work presents a streamlined approach for realizing aqueous zinc-ion batteries with extended service life.展开更多
Regulating lithium(Li)salt decomposition to construct a stable solid electrolyte interphase(SEI)represents a pivotal strategy for mitigating Li dendrite and unlocking the full potential of polymer-based all-solid-stat...Regulating lithium(Li)salt decomposition to construct a stable solid electrolyte interphase(SEI)represents a pivotal strategy for mitigating Li dendrite and unlocking the full potential of polymer-based all-solid-state Li metal batteries.However,this approach necessitates precise manipulation of the coordination chemistry and decomposition kinetics of Li-salt anions,which remains a formidable challenge in the field.Herein,we unveil a molecular docking-guided design framework that correlates the molecular topology of ligands with bis(trifluoromethanesulfonyl)imide(TFSI-)anion coordination chemistry in poly(ethylene oxide)(PEO)-based solid polymer electrolytes.Theoretical calculations and experimental investigations elucidate that short-chain dithiols(e.g.,1,2-ethanedithiol,C2)exhibit optimal spatial complementarity and superior molecular docking efficacy with TFSI-compared to long-chain analogues.Intermolecular hydrogen bonding redistributes electron density toward TFSI-,promoting its decomposition and enhancing LiF content in the SEI,thereby effectively suppressing Li dendrite growth.Consequently,the Li||LiFePO_(4)cells equipped with PEO-LiTFSI-C2 electrolyte achieve a remarkable 99.2%capacity retention after 580 cycles at 1.0 C,surpassing both long-chain dithiol systems and most previously reported electrolytes.This work provides mechanistic insights into the anion-coordination-mediated SEI formation process.Furthermore,the molecular docking is expected to play a significant role in understanding and researching the interfacial chemistry of allsolid-state Li metal batteries.展开更多
Solid-state lithium metal batteries(SSLMBs)face critical challenges from dendrite growth and unstable interfaces.While composite polymer electrolytes(CPEs)offer promise,poor ionic conductivity(<10^(-5)S cm^(-1)),lo...Solid-state lithium metal batteries(SSLMBs)face critical challenges from dendrite growth and unstable interfaces.While composite polymer electrolytes(CPEs)offer promise,poor ionic conductivity(<10^(-5)S cm^(-1)),low Li^(+)transference numbers(t_(Li^(+))<0.5),and inadequate interfacial stability limit practical application.Herein,we design a dual-channel metal-organic framework(MOF)-based CPEs that simultaneously regulate ion transport and construct a high-conductivity interphase.This MOF features two distinct channels.The one imposes spatial confinement(0.57 nm in pore size)to suppress anion migration(TFSI-),while the other facilitates immobilizing TFSI^(-)through iodine-mediated nucleophilic substitution.More importantly,the liberated I^(-)reacts with Li^(+)to in situ generate lithium iodide(LiI)-enhanced solid-electrolyte interphase(SEI),replacing insulating LiF-rich counterparts.This Lil-SEI exhibits superior ionic conductivity and homogenizes Li^(+)flux to suppress dendrites.Integrated into a poly(vinylidene fluoride)-cohexafluoropropylene(PVDF-HFP)matrix,the MOF CPE achieves exceptional ionic conductivity(2.13×10^(-4)S cm^(-1))and a high t_(Li^(+))of 0.95(25℃).Density functional theory and molecular dynamics calculations verify ion-regulation mechanisms.As a result,LiFePO_(4)//Li cells retain 94.99%capacity after 800 cycles(1 C),while NCM811//Li cells demonstrate sustained stability over 200 cycles.This work provides valuable insights into the design of multifunctional MOF ionic conductors for highperformance SSLMBs.展开更多
基金financially supported by the National Natural Science Foundation of China(Grant No.22075331,21905057)。
文摘Solid electrolyte interphase(SEI)is widely acknowledged as the most crucial and least comprehended component in secondary batteries.Particularly,fluorinated SEI derived from the decomposition of fluorinated salt/solvent electrolyte or additive has been widely applied to extend the lifespan of Li/Na anodes,and a similar strategy is being implemented for Zn metal electrodes.However,fluorine-containing electrolytes raise concerns regarding cost,toxicity,corrosivity,and environmental contamination.Moreover,the necessity and role of fluorine in the SEI component remain unclear,particularly in the aqueous system.Here,we report a fluorine-free inorganic-rich SEI layer in situ built by introducing a low-cost,low-concentration tetraethyl ammonium iodide(TEAI)into dilute aqueous ZnSO_(4)electrolyte.The TEAI additive is found to simultaneously modulate the Zn^(2+)solvation structure and optimize the chemisorption at the anode/electrolyte interface.The synergistic interaction between the I-/SO_(4)^(2-)anion-involved solvation structure and adsorbed TEA^(+)cations drives the formation of fluorine-free SEI with inorganics(Zn_(3)N_(2),Zn(IO_(3))_(2),Zn S,etc.),which are capable of providing fast Zn^(2+)transport ability,high-flux nucleation site,and preferential Zn(002)deposition.Besides the reductive decomposition with the formation of Irich SEI layer,the redox-active iodine species can rejuvenate inactive byproducts and dead Zn,allowing the interface self-healing and ensuring long-term interfacial stability.The TEAI-formulated electrolyte endows the Zn anode with excellent Zn reversibility by achieving dendrite-free Zn plating/stripping over 6500 h in the Zn||Zn symmetric battery at 1 mA cm^(-2).This study provides new insights into stabilizing Zn metal electrodes via robust fluorine-free interphases.
基金funded by the National Natural Science Foundation of China(Nos.22179098 and 22209153).
文摘Despite its high capacity behavior as the anode for lithium-ion batteries (LIBs), SnO_(2) suffers the poorelectronic conductivity and high volume expansion, which lead to poor cycling stability and rate capability. In this study, we employ defect engineering to design SnO_(2−x)(x = 0, 0.12, 0.2, and 0.3) nanoparticleswith varied oxygen vacancies. Notably, the SnO1.80 electrode with 20 % oxygen vacancies exhibits excellent electrochemical performance. Advanced physical characterizations combined with density functionaltheory (DFT) simulations demonstrate that the improved electrochemical performance can be attributedto the formation of a stable, uniform, and LiF-rich solid-electrolyte interface (SEI) layer through the optimization of oxygen vacancies. This study shows novel insights into the application of defect engineeringwithin oxides for the rational design of the uniform surface layer toward high-energy-density LIBs.
基金supported by the National Natural Science Foundation of China(52272258 and 52411530056)the Beijing Nova Program(20220484214)+1 种基金Key R&D and Transformation Projects in Qinghai Province(2023-HZ-801)the financial support from the China Scholarship Council(No.202006210070)。
文摘Aqueous zinc-ion batteries encounter impediments on their trajectory towards commercialization,primarily due to challenges such as dendritic growth,hydrogen evolution reaction.Throughout recent decades of investigation,electrolyte modulation by using function additives is widely considered as a facile and efficient way to prolong the Zn anode lifespan.Herein,N-(2-hydroxypropyl)ethylenediamine is employed as an additive to attach onto the Zn surface with a substantial adsorption energy with(002)facet.The as-formed in-situ solid-electrolyte interphase layer effectively mitigates hydrogen evolution reaction by constructing a lean-water internal Helmholtz layer.Additionally,N-(2-hydroxypropyl)ethylenediamine establishes a coordination complex with Zn^(2+),thereby modulating the solvation structure and enhancing the mobility of Zn^(2+).As expected,the Zn-symmetrical cell with N-(2-hydroxypropyl)ethylenediamine additive demonstrated successful cycling exceeding 1500 h under 1 mA cm^(-2) for0.5 mAh cm^(-2).Furthermore,the Zn//δ-MnO_(2) battery maintains a capacity of approximately 130 mAh g^(-1) after 800 cycles at 1 A g^(-1),with a Coulombic efficiency surpassing 98%.This work presents a streamlined approach for realizing aqueous zinc-ion batteries with extended service life.
基金financial support from the National Natural Science Foundation of China(grants 52225208,52171225,U21A20174,52222317)the Energy Revolution S&T Program of Yulin Innovation Institute of Clean Energy(grant E411010316)+1 种基金the “Pioneer”and “Leading Goose”R&D Program of Zhejiang(grants 2025C01157,2025C01182)the Natural Science Foundation of Zhejiang province(grants LZ24E020006,LQN25B030005)。
文摘Regulating lithium(Li)salt decomposition to construct a stable solid electrolyte interphase(SEI)represents a pivotal strategy for mitigating Li dendrite and unlocking the full potential of polymer-based all-solid-state Li metal batteries.However,this approach necessitates precise manipulation of the coordination chemistry and decomposition kinetics of Li-salt anions,which remains a formidable challenge in the field.Herein,we unveil a molecular docking-guided design framework that correlates the molecular topology of ligands with bis(trifluoromethanesulfonyl)imide(TFSI-)anion coordination chemistry in poly(ethylene oxide)(PEO)-based solid polymer electrolytes.Theoretical calculations and experimental investigations elucidate that short-chain dithiols(e.g.,1,2-ethanedithiol,C2)exhibit optimal spatial complementarity and superior molecular docking efficacy with TFSI-compared to long-chain analogues.Intermolecular hydrogen bonding redistributes electron density toward TFSI-,promoting its decomposition and enhancing LiF content in the SEI,thereby effectively suppressing Li dendrite growth.Consequently,the Li||LiFePO_(4)cells equipped with PEO-LiTFSI-C2 electrolyte achieve a remarkable 99.2%capacity retention after 580 cycles at 1.0 C,surpassing both long-chain dithiol systems and most previously reported electrolytes.This work provides mechanistic insights into the anion-coordination-mediated SEI formation process.Furthermore,the molecular docking is expected to play a significant role in understanding and researching the interfacial chemistry of allsolid-state Li metal batteries.
基金financial support from the National Natural Science Foundation of China(22271178,U2032131,21972103)the International Cooperation Key Project of Science and Technology Department of Shaanxi,China(2022KWZ-06)+4 种基金the Youth Talent Promotion Project of Science and Technology Association of Universities of Shaanxi Province(20210602)the Research project of Xi'an Science and Technology Bureau(2022GXFW0011)the Science and Technology New Star in Shaanxi Province(2023 KJXX-045)the Shaanxi Provincial Department of Education service local special project,industrialization cultivation project(23JC007)The Natural Science Basic Research Plan in Shaanxi Province of China[2024JC-YBMS-445]。
文摘Solid-state lithium metal batteries(SSLMBs)face critical challenges from dendrite growth and unstable interfaces.While composite polymer electrolytes(CPEs)offer promise,poor ionic conductivity(<10^(-5)S cm^(-1)),low Li^(+)transference numbers(t_(Li^(+))<0.5),and inadequate interfacial stability limit practical application.Herein,we design a dual-channel metal-organic framework(MOF)-based CPEs that simultaneously regulate ion transport and construct a high-conductivity interphase.This MOF features two distinct channels.The one imposes spatial confinement(0.57 nm in pore size)to suppress anion migration(TFSI-),while the other facilitates immobilizing TFSI^(-)through iodine-mediated nucleophilic substitution.More importantly,the liberated I^(-)reacts with Li^(+)to in situ generate lithium iodide(LiI)-enhanced solid-electrolyte interphase(SEI),replacing insulating LiF-rich counterparts.This Lil-SEI exhibits superior ionic conductivity and homogenizes Li^(+)flux to suppress dendrites.Integrated into a poly(vinylidene fluoride)-cohexafluoropropylene(PVDF-HFP)matrix,the MOF CPE achieves exceptional ionic conductivity(2.13×10^(-4)S cm^(-1))and a high t_(Li^(+))of 0.95(25℃).Density functional theory and molecular dynamics calculations verify ion-regulation mechanisms.As a result,LiFePO_(4)//Li cells retain 94.99%capacity after 800 cycles(1 C),while NCM811//Li cells demonstrate sustained stability over 200 cycles.This work provides valuable insights into the design of multifunctional MOF ionic conductors for highperformance SSLMBs.
