1.Indroduction In light of the global transition toward carbon neutrality,the development of mild-condition ammonia synthesis technologies has gained significant attention as a promising solution to address the inhere...1.Indroduction In light of the global transition toward carbon neutrality,the development of mild-condition ammonia synthesis technologies has gained significant attention as a promising solution to address the inherent limitations of the traditional Haber-Bosch approach,which remains highly energy-intensive due to the extreme operation conditions(above 350℃ and over 10 MPa)required to activate the robust N≡N bond(945 kJ mol-1).Furthermore,the process is carbon-intensive,as its primary hydrogen source is derived from hydrocarbon reforming with high carbon emissions[1,2].展开更多
The ineluctable introduction of lithium salt to polymer solid-state electrolytes incurs a compromise between strength,ionic conductivity,and thickness.Here,we propose Al2O3-coated polyimide(AO/PI)porous film as ...The ineluctable introduction of lithium salt to polymer solid-state electrolytes incurs a compromise between strength,ionic conductivity,and thickness.Here,we propose Al2O3-coated polyimide(AO/PI)porous film as a high-strength substrate to support fast-ion-conducting polymer-in-salt(PIS)solid-state electrolytes,aiming to suppress lithium dendrite growth and improve full-cell performance.The Al2O3coating layer not only refines the wettability of polyimide porous film to PIS,but also performs as a high modulus protective layer to suppress the growth of lithium dendrites.The resulting PI/AO@PIS exhibits a small thickness of only 35μm with an outstanding tensile strength of 11.3 MPa and Young's modulus of 537.6 MPa.In addition,the PI/AO@PIS delivers a high ionic conductivity of 0.1 m S/cm at 25°C.As a result,the PI/AO@PIS enables symmetric Li cells to achieve exceptional cyclability for over 1000 h at 0.1 m A/cm2without noticeable lithium dendrite formation.Moreover,the PI/AO@PIS-based LiFePO4||Li full cells demonstrate outstanding rate performance(125.7 m Ah/g at 5 C)and impressive cycling stability(96.1%capacity retention at 1 C after 200 cycles).This work highlights the efficacy of enhancing the mechanical properties of polymer matrices and extending cell performance through the incorporation of a dense inorganic interface layer.展开更多
ZnO with good lithiophilicity has widely been employed to modify the lithiophobic substrates and facilitate uniform lithium(Li)deposition.The overpotential of ZnO-derived Li anode during cycling depends on the lithiop...ZnO with good lithiophilicity has widely been employed to modify the lithiophobic substrates and facilitate uniform lithium(Li)deposition.The overpotential of ZnO-derived Li anode during cycling depends on the lithiophilicity of both LiZn and Li2O products upon lithiation of ZnO.However,the striking differences in the lithiophilicity between Li2O and LiZn would result in a high overpotential during cycling.In this research,the Al2O3ZnO(n≥1)hybrid layers were precisely fabricated by atomic layer deposition(ALD)to regulate the lithiophilicity of ZnO phase and Li2O/LiZn configuration—determining the actual Li loading amount and Li plating/stripping processes.Theoretically,the Li adsorption energy(Ea)values of LiZn and Li2O in the LiZn/Li2O configuration are separately predicted as-2.789 and-3.447 eV.In comparison,the Ea values of LiZn,LiAlO2,and Li2O in the LiZn/LiAlO2/Li2O configuration upon lithiation of Al2O3/8ZnO layer are calculated as-2.899,-3.089,and-3.208 eV,respectively.Importantly,a novel introduction of LiAlO2into the LiZn/Li2O configuration could enable the hierarchical Li plating/stripping and reduce the overpotentials during cycling.Consequently,the Al2O3/8ZnO-derived hybrid Li-metal anode could exhibit electrochemical performances superior to these of ZnO-derived Li anode in both symmetrical and full cells paired with a LiNi0.6Co0.2Mn0.2O2(NCM622)cathode.展开更多
Ni-rich cathodes(Ni≥70%)with high specific capacities emerge as promising candidates for long-range lithium-ion batteries(LIBs).Nevertheless,their practical application is severely limited by two unresolved challenge...Ni-rich cathodes(Ni≥70%)with high specific capacities emerge as promising candidates for long-range lithium-ion batteries(LIBs).Nevertheless,their practical application is severely limited by two unresolved challenges:structural degradation from uncontrolled Li/Ni mixing and interfacial instability exacerbated by air/electrolyte corrosion.Herein,we propose a dual-modulation strategy to synthesize a stable Ni-rich cathode via carboxylate-based metal-organic frameworks(MOFs)-derived precursors,whereby oxygen vacancies in the precursors induce controlled moderate Li/Ni mixing,while their enhanced specific-surface-area property enables dense amorphous Li2CO3encapsulation.The optimal Li/Ni mixing harnesses the Ni pillar effect to stabilize the structure of cathodes upon cycling.Additionally,amorphous Li2CO3coating serves not only as a thermodynamically stable and air-impermeable protective layer for the cathodes,but as a transformative precursor for an F-rich cathode electrolyte interphase(CEI)which enhances interfacial stability and electrochemical properties.This dual-modulated cathode delivers a high discharge capacity of 215.1 mA h g-1at 0.1 C,retains 84.9% capacity after 200 cycles at 1 C in half cells,and achieves 96.0 mA h g-1at 8 C in full-cell tests.Furthermore,we unravel the potential mechanism of Ni pillar effect from optimal Li/Ni mixing and track the evolution mechanism of Li2CO3coating into F-rich CEI.This work offers advanced perspectives for the controllable cation disordering engineering and rational design of surface residual lithium compounds in Ni-rich cathodes,thereby providing new guiding principles for protecting high-capacity cathodes in energy storage devices.展开更多
Sodium titanium phosphate(NaTi2(PO4)3,NTP)has emerged as a promising electrode material due to its three-dimensional open framework.This study investigates the use of NTP in aqueous dilute Li+/Na+electr...Sodium titanium phosphate(NaTi2(PO4)3,NTP)has emerged as a promising electrode material due to its three-dimensional open framework.This study investigates the use of NTP in aqueous dilute Li+/Na+electrolytes and extends its application to high-concentration K+electrolytes.X-ray photoelectron spectroscopy,X-ray absorption near-edge structure analysis,and density functional theory calculations revealed that highly electronegative fluorine partially substitutes for oxygen in the NTP lattice,resulting in the formation of Ti-F bonds.The substitution effectively modulates the electronic structure of Ti4+,alters the local coordination environment,and influences the redox dynamics.Enhanced long-term cycling stability and rate performance were demonstrated across aqueous sodium-ion,lithium-ion,and potassium-ion half-cells.Among the investigated systems,the aqueous sodium-ion system exhibited the best electrochemical performance,characterized by a single,well-defined charge–discharge plateau,stable cycling behavior with 88.7%capacity retention after 500 cycles at 1 A g−1,and an initial specific discharge capacity of 121.7 mAh g−1 at 0.2 A g−1.The results establish F-doped NTP as a promising candidate for advanced energy storage applications in aqueous alkali metal-ion batteries.展开更多
基金the financial support from the National Natural Science Foundation of China(Nos.22588201,22225204 to D.D.,22472169 to L.Y.,and 22427801 to W.L.)the Outstanding Member of CAS Youth Innovation Promotion Association(No.Y2023053 to W.L.)the DICP&SIA Joint Project(No.UN202401 to W.L.)。
摘要1.Indroduction In light of the global transition toward carbon neutrality,the development of mild-condition ammonia synthesis technologies has gained significant attention as a promising solution to address the inherent limitations of the traditional Haber-Bosch approach,which remains highly energy-intensive due to the extreme operation conditions(above 350℃ and over 10 MPa)required to activate the robust N≡N bond(945 kJ mol-1).Furthermore,the process is carbon-intensive,as its primary hydrogen source is derived from hydrocarbon reforming with high carbon emissions[1,2].
基金the financial support from the 261Project of MIIT and Natural Science Foundation of Jiangsu Province(No.BK20240179)。
摘要The ineluctable introduction of lithium salt to polymer solid-state electrolytes incurs a compromise between strength,ionic conductivity,and thickness.Here,we propose Al2O3-coated polyimide(AO/PI)porous film as a high-strength substrate to support fast-ion-conducting polymer-in-salt(PIS)solid-state electrolytes,aiming to suppress lithium dendrite growth and improve full-cell performance.The Al2O3coating layer not only refines the wettability of polyimide porous film to PIS,but also performs as a high modulus protective layer to suppress the growth of lithium dendrites.The resulting PI/AO@PIS exhibits a small thickness of only 35μm with an outstanding tensile strength of 11.3 MPa and Young's modulus of 537.6 MPa.In addition,the PI/AO@PIS delivers a high ionic conductivity of 0.1 m S/cm at 25°C.As a result,the PI/AO@PIS enables symmetric Li cells to achieve exceptional cyclability for over 1000 h at 0.1 m A/cm2without noticeable lithium dendrite formation.Moreover,the PI/AO@PIS-based LiFePO4||Li full cells demonstrate outstanding rate performance(125.7 m Ah/g at 5 C)and impressive cycling stability(96.1%capacity retention at 1 C after 200 cycles).This work highlights the efficacy of enhancing the mechanical properties of polymer matrices and extending cell performance through the incorporation of a dense inorganic interface layer.
基金supported by the National Key Research and Development Program of China(2021YFB2400202)the National Natural Science Foundation of China(52104313)+1 种基金the Key Research and Development Plan of Shaanxi(2024GH-YBXM-11)the Foshan Science and Technology Innovation Team Project(1920001004098).
摘要ZnO with good lithiophilicity has widely been employed to modify the lithiophobic substrates and facilitate uniform lithium(Li)deposition.The overpotential of ZnO-derived Li anode during cycling depends on the lithiophilicity of both LiZn and Li2O products upon lithiation of ZnO.However,the striking differences in the lithiophilicity between Li2O and LiZn would result in a high overpotential during cycling.In this research,the Al2O3ZnO(n≥1)hybrid layers were precisely fabricated by atomic layer deposition(ALD)to regulate the lithiophilicity of ZnO phase and Li2O/LiZn configuration—determining the actual Li loading amount and Li plating/stripping processes.Theoretically,the Li adsorption energy(Ea)values of LiZn and Li2O in the LiZn/Li2O configuration are separately predicted as-2.789 and-3.447 eV.In comparison,the Ea values of LiZn,LiAlO2,and Li2O in the LiZn/LiAlO2/Li2O configuration upon lithiation of Al2O3/8ZnO layer are calculated as-2.899,-3.089,and-3.208 eV,respectively.Importantly,a novel introduction of LiAlO2into the LiZn/Li2O configuration could enable the hierarchical Li plating/stripping and reduce the overpotentials during cycling.Consequently,the Al2O3/8ZnO-derived hybrid Li-metal anode could exhibit electrochemical performances superior to these of ZnO-derived Li anode in both symmetrical and full cells paired with a LiNi0.6Co0.2Mn0.2O2(NCM622)cathode.
基金the financial support from the Special Funds for the Cultivation of Guangdong College Students’Scientific and Technological Innovation(“Climbing Program”Special Funds,pdjh2024a109)。
摘要Ni-rich cathodes(Ni≥70%)with high specific capacities emerge as promising candidates for long-range lithium-ion batteries(LIBs).Nevertheless,their practical application is severely limited by two unresolved challenges:structural degradation from uncontrolled Li/Ni mixing and interfacial instability exacerbated by air/electrolyte corrosion.Herein,we propose a dual-modulation strategy to synthesize a stable Ni-rich cathode via carboxylate-based metal-organic frameworks(MOFs)-derived precursors,whereby oxygen vacancies in the precursors induce controlled moderate Li/Ni mixing,while their enhanced specific-surface-area property enables dense amorphous Li2CO3encapsulation.The optimal Li/Ni mixing harnesses the Ni pillar effect to stabilize the structure of cathodes upon cycling.Additionally,amorphous Li2CO3coating serves not only as a thermodynamically stable and air-impermeable protective layer for the cathodes,but as a transformative precursor for an F-rich cathode electrolyte interphase(CEI)which enhances interfacial stability and electrochemical properties.This dual-modulated cathode delivers a high discharge capacity of 215.1 mA h g-1at 0.1 C,retains 84.9% capacity after 200 cycles at 1 C in half cells,and achieves 96.0 mA h g-1at 8 C in full-cell tests.Furthermore,we unravel the potential mechanism of Ni pillar effect from optimal Li/Ni mixing and track the evolution mechanism of Li2CO3coating into F-rich CEI.This work offers advanced perspectives for the controllable cation disordering engineering and rational design of surface residual lithium compounds in Ni-rich cathodes,thereby providing new guiding principles for protecting high-capacity cathodes in energy storage devices.
基金supported by the National Natural Science Foundation of China(52072298,51802261,11675129)the Natural Science Basic Research Plan in Shaanxi Province of China(2025JC-YBQN-758)+1 种基金Scientific Research Program Funded by Shaanxi Provincial Education Department(Program No.23JK0662)the Youth Innovation Team of Shaanxi Universities.
摘要Sodium titanium phosphate(NaTi2(PO4)3,NTP)has emerged as a promising electrode material due to its three-dimensional open framework.This study investigates the use of NTP in aqueous dilute Li+/Na+electrolytes and extends its application to high-concentration K+electrolytes.X-ray photoelectron spectroscopy,X-ray absorption near-edge structure analysis,and density functional theory calculations revealed that highly electronegative fluorine partially substitutes for oxygen in the NTP lattice,resulting in the formation of Ti-F bonds.The substitution effectively modulates the electronic structure of Ti4+,alters the local coordination environment,and influences the redox dynamics.Enhanced long-term cycling stability and rate performance were demonstrated across aqueous sodium-ion,lithium-ion,and potassium-ion half-cells.Among the investigated systems,the aqueous sodium-ion system exhibited the best electrochemical performance,characterized by a single,well-defined charge–discharge plateau,stable cycling behavior with 88.7%capacity retention after 500 cycles at 1 A g−1,and an initial specific discharge capacity of 121.7 mAh g−1 at 0.2 A g−1.The results establish F-doped NTP as a promising candidate for advanced energy storage applications in aqueous alkali metal-ion batteries.