The unprecedented growth of electric vehicles featuring lithium-ion batteries has led to a significant increase in the amount of waste generated,posing pressing waste management challenges for both industry professio ...The unprecedented growth of electric vehicles featuring lithium-ion batteries has led to a significant increase in the amount of waste generated,posing pressing waste management challenges for both industry professio nals and environmental regulators.To address these issues,conventio nal pyrometallurgical,hydrometallurgical,and direct recycling methods are commonly employed to promote sustainable battery development.However,these methods are often hindered by laborious purification processes and the generation of low-profit products such as Li_(2)CO_(3),CoSO_(4),NiSO_(4),etc.Herein,an upcycling technology involving a low-temperature solid-to-solid reaction and water leaching procedures is introduced to transform spent LiCoO_(2)cathode materials into value-added cobalt sulfide-based electrocatalysts.The regenerated electrocatalysts exhibit exceptional performance in the oxygen evolution reaction,surpassing that of the benchmark RuO_(2)catalyst.This proposed upcycling method provides researchers with an alternative way to convert the metallic components of waste lithium-ion batteries into high-value Co-,Ni-,Fe-,and Mn-based catalysts.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 Al_(2)O_(3)-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 Al_(2)O_(3)-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 Al_(2)O_(3)coating 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 Li_(2)O products upon lithiation of ZnO.However,the striking differences in the lithiophilicity between Li_(2)O and LiZn would result in a high overpotential during cycling.In this research,the Al_(2)O_(3)/nZnO(n≥1)hybrid layers were precisely fabricated by atomic layer deposition(ALD)to regulate the lithiophilicity of ZnO phase and Li_(2)O/LiZn configuration—determining the actual Li loading amount and Li plating/stripping processes.Theoretically,the Li adsorption energy(E_(a))values of LiZn and Li_(2)O in the LiZn/Li_(2)O configuration are separately predicted as-2.789 and-3.447 eV.In comparison,the E_(a) values of LiZn,LiAlO_(2),and Li_(2)O in the LiZn/LiAlO_(2)/Li_(2)O configuration upon lithiation of Al_(2)O_(3)/8ZnO layer are calculated as-2.899,-3.089,and-3.208 eV,respectively.Importantly,a novel introduction of LiAlO_(2)into the LiZn/Li_(2)O configuration could enable the hierarchical Li plating/stripping and reduce the overpotentials during cycling.Consequently,the Al_(2)O_(3)/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 LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)(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 Li_(2)CO_(3)encapsulation.The optimal Li/Ni mixing harnesses the Ni pillar effect to stabilize the structure of cathodes upon cycling.Additionally,amorphous Li_(2)CO_(3)coating 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^(-1)at 0.1 C,retains 84.9% capacity after 200 cycles at 1 C in half cells,and achieves 96.0 mA h g^(-1)at 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 Li_(2)CO_(3)coating 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(NaTi_(2)(PO_(4))_(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(NaTi_(2)(PO_(4))_(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 Ti^(4+),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
H2TiO3 was obtained from the acid-modified adsorbent precursor Li2TiO3,which was synthesized by a solid-phase reaction between TiO2 and Li2CO3.The extraction ratio of Li＋ from Li2TiO3 was 98.86%,almost with no Ti4＋ ...H2TiO3 was obtained from the acid-modified adsorbent precursor Li2TiO3,which was synthesized by a solid-phase reaction between TiO2 and Li2CO3.The extraction ratio of Li＋ from Li2TiO3 was 98.86%,almost with no Ti4＋ extracted.The effects of lithium titanium ratio,calcining temperature and time were investigated on the synthesis of Li2TiO3.Li2TiO3,H2TiO3 and the adsorbed Li＋ adsorbent were characterized by XRD and SEM.The lithium adsorption properties were investigated by the adsorption kinetics and adsorption isotherm.The results indicate that H2TiO3 has an excellent adsorptive capacity for Li＋.Two simplified kinetic models including the pseudo-first-order and pseudo-second-order equations were selected to follow the adsorption processes.The rate constants of adsorption for these kinetic models were calculated.The results show that the adsorption process can be described by the pseudo-second-order equation,and the process is proved to be a chemical adsorption.The adsorption process that H2TiO3 adsorbs Li＋ in LiCl solution well fits the Langmuir equation with monolayer adsorption.展开更多
基金financial support from the National Natural Science Foundation of China(21702143,52303092)Talent Recruitment Project of Guangdong Province(No.2023QN10X078)+1 种基金Open Project of Yunnan Precious Metals Laboratory Co.,Ltd(No.YPML-2023050278)Guangdong Basic and Applied Basic Research Foundation Special Projects——GuangdongShenzhen Joint Funds(2022A1515110027)。
文摘The unprecedented growth of electric vehicles featuring lithium-ion batteries has led to a significant increase in the amount of waste generated,posing pressing waste management challenges for both industry professio nals and environmental regulators.To address these issues,conventio nal pyrometallurgical,hydrometallurgical,and direct recycling methods are commonly employed to promote sustainable battery development.However,these methods are often hindered by laborious purification processes and the generation of low-profit products such as Li_(2)CO_(3),CoSO_(4),NiSO_(4),etc.Herein,an upcycling technology involving a low-temperature solid-to-solid reaction and water leaching procedures is introduced to transform spent LiCoO_(2)cathode materials into value-added cobalt sulfide-based electrocatalysts.The regenerated electrocatalysts exhibit exceptional performance in the oxygen evolution reaction,surpassing that of the benchmark RuO_(2)catalyst.This proposed upcycling method provides researchers with an alternative way to convert the metallic components of waste lithium-ion batteries into high-value Co-,Ni-,Fe-,and Mn-based catalysts.
基金the financial support from the 261Project of MIIT and Natural Science Foundation of Jiangsu Province(No.BK20240179)。
文摘The ineluctable introduction of lithium salt to polymer solid-state electrolytes incurs a compromise between strength,ionic conductivity,and thickness.Here,we propose Al_(2)O_(3)-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 Al_(2)O_(3)coating 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).
文摘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 Li_(2)O products upon lithiation of ZnO.However,the striking differences in the lithiophilicity between Li_(2)O and LiZn would result in a high overpotential during cycling.In this research,the Al_(2)O_(3)/nZnO(n≥1)hybrid layers were precisely fabricated by atomic layer deposition(ALD)to regulate the lithiophilicity of ZnO phase and Li_(2)O/LiZn configuration—determining the actual Li loading amount and Li plating/stripping processes.Theoretically,the Li adsorption energy(E_(a))values of LiZn and Li_(2)O in the LiZn/Li_(2)O configuration are separately predicted as-2.789 and-3.447 eV.In comparison,the E_(a) values of LiZn,LiAlO_(2),and Li_(2)O in the LiZn/LiAlO_(2)/Li_(2)O configuration upon lithiation of Al_(2)O_(3)/8ZnO layer are calculated as-2.899,-3.089,and-3.208 eV,respectively.Importantly,a novel introduction of LiAlO_(2)into the LiZn/Li_(2)O configuration could enable the hierarchical Li plating/stripping and reduce the overpotentials during cycling.Consequently,the Al_(2)O_(3)/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 LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)(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)。
文摘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 Li_(2)CO_(3)encapsulation.The optimal Li/Ni mixing harnesses the Ni pillar effect to stabilize the structure of cathodes upon cycling.Additionally,amorphous Li_(2)CO_(3)coating 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^(-1)at 0.1 C,retains 84.9% capacity after 200 cycles at 1 C in half cells,and achieves 96.0 mA h g^(-1)at 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 Li_(2)CO_(3)coating 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.
文摘Sodium titanium phosphate(NaTi_(2)(PO_(4))_(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 Ti^(4+),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.
基金Project(2008BAB35B04) supported by the National Key Technologies R&D Program of ChinaProject(2010QZZD003) supported by Central South University Advanced Research Program,China
文摘H2TiO3 was obtained from the acid-modified adsorbent precursor Li2TiO3,which was synthesized by a solid-phase reaction between TiO2 and Li2CO3.The extraction ratio of Li＋ from Li2TiO3 was 98.86%,almost with no Ti4＋ extracted.The effects of lithium titanium ratio,calcining temperature and time were investigated on the synthesis of Li2TiO3.Li2TiO3,H2TiO3 and the adsorbed Li＋ adsorbent were characterized by XRD and SEM.The lithium adsorption properties were investigated by the adsorption kinetics and adsorption isotherm.The results indicate that H2TiO3 has an excellent adsorptive capacity for Li＋.Two simplified kinetic models including the pseudo-first-order and pseudo-second-order equations were selected to follow the adsorption processes.The rate constants of adsorption for these kinetic models were calculated.The results show that the adsorption process can be described by the pseudo-second-order equation,and the process is proved to be a chemical adsorption.The adsorption process that H2TiO3 adsorbs Li＋ in LiCl solution well fits the Langmuir equation with monolayer adsorption.
