Regulating lithium(Li)plating/stripping behavior in three-dimensional(3D)conductive scaffolds is critical to stabilizing Li metal batteries(LMBs).Surface protrusions and roughness in these scaffolds can induce uneven ...Regulating lithium(Li)plating/stripping behavior in three-dimensional(3D)conductive scaffolds is critical to stabilizing Li metal batteries(LMBs).Surface protrusions and roughness in these scaffolds can induce uneven distributions of the electric fields and ionic concentrations,forming“hot spots.”Hot spots may cause uncontrollable Li dendrites growth,presenting significant challenges to the cycle stability and safety of LMBs.To address these issues,we construct a Li ionic conductive-dielectric gradient bifunctional interlayer(ICDL)onto a 3D Li-injected graphene/carbon nanotube scaffold(LGCF)via in situ reaction of exfoliated hexagonal boron nitride(fhBN)and molten Li.Microscopic and spectroscopic analyses reveal that ICDL consists of fhBN-rich outer layer and inner layer enriched with Li_(3)N and Li-boron composites(Li-B).The outer layer utilizes dielectric properties to effectively homogenize the electric field,while the inner layer ensures high Li ion conductivity.Moreover,DFT calculations indicate that ICDL can effectively adsorb Li and decrease the Li diffusion barrier,promoting enhanced Li ion transport.The modulation of Li kinetics by ICDL increases the critical length of the Li nucleus,enabling suppression of Li dendrite growth.Attributing to these advantages,the ICDL-coated LGCF(ICDL@LGCF)demonstrates impressive long-term cycle performances in both symmetric cells and full cells.展开更多
A pseudocapacitance dominated anode material assembled from Li_(3)VO_(4)nanocrystals encapsulated in the interlayers of N-doped graphene has been developed via a facile 2D nanospace confined strategy for lithium ion c...A pseudocapacitance dominated anode material assembled from Li_(3)VO_(4)nanocrystals encapsulated in the interlayers of N-doped graphene has been developed via a facile 2D nanospace confined strategy for lithium ion capacitors(LICs).In this contribution,the N-doped graphene synthesized by a faicle solid state reaction using C_(3)N_(4)nanosheets as template and glucose as carbon source provides sufficient 2D nanospace for the confined and homogeneous growth of Li_(3)VO_(4)at the nanoscale,and simultaneously efficiently anchors each nanobuilding block inside the interlayers,thus realizing the utilizaiton of full potential of active components.The so-formed 3D hybrids not only ensure intimate electronic coupling between active materials and N-doped graphene,but also realize robust structure integrity.Owing to these unique advantages,the resulting hybrids show pseudocapacitance dominated lithium storage behaviors with capacitive contributions of over 90%at both low and high current rates.The LVO@C@NG delivers reversible capacities of 206 mAh/g at 10 A/g,capacity retention of 92.7%after 1000 cycles at 2 A/g,and a high energy density of 113.6 Wh/kg at 231.8 W/kg for LICs.展开更多
The rapid advancement of energy storage technologies highlights the urgent need for innovative electrochemical energy storage(EES)systems featuring complex geometries.Three-dimensional(3D)printing has emerged as a gro...The rapid advancement of energy storage technologies highlights the urgent need for innovative electrochemical energy storage(EES)systems featuring complex geometries.Three-dimensional(3D)printing has emerged as a groundbreaking solution,enabling the fabrication of customized,high-performance electrodes with precise structural control.This approach enhances accuracy,convenience,and facilitates improved ion and electron transport.In this review,we systematically summarize recent advancements in leveraging 3D printing techniques for lithium-ion and sodium-ion batteries.We begin by comparing the unique capabilities of various 3D printing methods against traditional fabrication techniques for producing tailored electrodes.We then address critical challenges across different battery module architectures-cathodes,anodes,electrolytes,and integrated systems-highlighting breakthroughs in material selection,ink formulation,and post-processing.Finally,we explore the future potential of 3Dprinted batteries in next-generation EES devices,emphasizing their role in advancing customizable,high-efficiency solutions.The insights provided herein illuminate how 3D printing can significantly accelerate the development of advanced battery materials,fostering innovation in energy storage technology.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
Fully utilizing renewable biomass energy is important for saving energy,reducing carbon emissions,and mitigating climate change.As the main hydrolysate of cellulose,a primary component of lignocellulose,glucose could ...Fully utilizing renewable biomass energy is important for saving energy,reducing carbon emissions,and mitigating climate change.As the main hydrolysate of cellulose,a primary component of lignocellulose,glucose could be employed as a starting material to prepare some other functional derivatives for improving the value of biomass resources.The isomerization of glucose to produce fructose is an important intermediate process during numerous high-value-added chemical preparations.Therefore,the development of efficient and selective catalysts for glucose isomerization is of great significance.Currently,glucose isomerase catalysts are limited by the harsh conditions required for microbial activity,which restricts further improvements in fructose yield.Additionally,heterogeneous Bronsted-base and Lewis-acid catalysts commonly employed in chemical isomerization methods often lead to the formation of undesirable by-products,resulting in reduced selectivity toward fructose.This study has demonstrated that lithium-loaded heterogeneous catalysts possess excellent isomerization capabilities under mild conditions.A highly efficient Li-C_(3)N_(4) catalyst was developed,achieving a fructose selectivity of 99.9% and a yield of 42.6% at 60℃ within 1.0 h-comparable to the performance of the enzymatic method.Characterization using X-ray photoelectron spectroscopy(XPS),X-ray diffraction(XRD),proton nuclear magnetic resonance(^(1)H NMR),and inductively coupled plasma(ICP)analyses confirmed that lithium was stably incorporated into the g-C_(3)N_(4) framework through the formation of Li-N bonds.Further investigations using CO_(2) temperature-programmed desorption(CO_(2)-TPD),in situ Fourier-transform infrared spectroscopy(FT-IR)and 7Li magic angle spinning nuclear magnetic resonance(^(7)Li MAS NMR)indicated that the isomerization proceeded via a base-catalyzed mechanism.The Li species were found to interact with hydroxyl groups generated through hydrolysis and simultaneously coordinated with nitrogen atoms in the C_(3)N_(4) matrix,resulting in the formation of Li-N_(6)-H_(2)O active sites.These active sites facilitated the deprotonation of glucose to form an enolate intermediate,followed by a proton transfer step that generated fructose.This mechanism not only improved the efficiency of fructose production but also provided valuable insight into the catalytic role of lithium within the isomerization process.展开更多
基金the financial support from the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (NRF-2023R1A2C2007699 and 2022R1A6A1A0306303912)the Nano Material Technology Development Program through the NRF funded by the Ministry of Science and ICT (NRF-2015M3A7B6027970)the Technology Innovation Program by the Ministry of Trade, Industry & Energy (RS-202300236794)
文摘Regulating lithium(Li)plating/stripping behavior in three-dimensional(3D)conductive scaffolds is critical to stabilizing Li metal batteries(LMBs).Surface protrusions and roughness in these scaffolds can induce uneven distributions of the electric fields and ionic concentrations,forming“hot spots.”Hot spots may cause uncontrollable Li dendrites growth,presenting significant challenges to the cycle stability and safety of LMBs.To address these issues,we construct a Li ionic conductive-dielectric gradient bifunctional interlayer(ICDL)onto a 3D Li-injected graphene/carbon nanotube scaffold(LGCF)via in situ reaction of exfoliated hexagonal boron nitride(fhBN)and molten Li.Microscopic and spectroscopic analyses reveal that ICDL consists of fhBN-rich outer layer and inner layer enriched with Li_(3)N and Li-boron composites(Li-B).The outer layer utilizes dielectric properties to effectively homogenize the electric field,while the inner layer ensures high Li ion conductivity.Moreover,DFT calculations indicate that ICDL can effectively adsorb Li and decrease the Li diffusion barrier,promoting enhanced Li ion transport.The modulation of Li kinetics by ICDL increases the critical length of the Li nucleus,enabling suppression of Li dendrite growth.Attributing to these advantages,the ICDL-coated LGCF(ICDL@LGCF)demonstrates impressive long-term cycle performances in both symmetric cells and full cells.
基金financially supported by the National Natural Science Foundation of China(Nos.52001059,52072119)Hunan Provincial Natural Science Foundation(No.2023JJ50015)the 111 Project(No.D20015)。
文摘A pseudocapacitance dominated anode material assembled from Li_(3)VO_(4)nanocrystals encapsulated in the interlayers of N-doped graphene has been developed via a facile 2D nanospace confined strategy for lithium ion capacitors(LICs).In this contribution,the N-doped graphene synthesized by a faicle solid state reaction using C_(3)N_(4)nanosheets as template and glucose as carbon source provides sufficient 2D nanospace for the confined and homogeneous growth of Li_(3)VO_(4)at the nanoscale,and simultaneously efficiently anchors each nanobuilding block inside the interlayers,thus realizing the utilizaiton of full potential of active components.The so-formed 3D hybrids not only ensure intimate electronic coupling between active materials and N-doped graphene,but also realize robust structure integrity.Owing to these unique advantages,the resulting hybrids show pseudocapacitance dominated lithium storage behaviors with capacitive contributions of over 90%at both low and high current rates.The LVO@C@NG delivers reversible capacities of 206 mAh/g at 10 A/g,capacity retention of 92.7%after 1000 cycles at 2 A/g,and a high energy density of 113.6 Wh/kg at 231.8 W/kg for LICs.
基金financially supported by the National Natural Science Foundation of China(22225902,U22A20436,22209185)the National Key Research&Development Program of China(2022YFE0115900,2021YFA1501500)+2 种基金the China National Postdoctoral Program for Innovative Talents(BX20230365)the China Postdoctoral Science Foundation(2023M743494)Self-Deployment Project Research Program of Haixi Institutes,Chinese Academy of Sciences(CXZX-2023-JQ08)。
文摘The rapid advancement of energy storage technologies highlights the urgent need for innovative electrochemical energy storage(EES)systems featuring complex geometries.Three-dimensional(3D)printing has emerged as a groundbreaking solution,enabling the fabrication of customized,high-performance electrodes with precise structural control.This approach enhances accuracy,convenience,and facilitates improved ion and electron transport.In this review,we systematically summarize recent advancements in leveraging 3D printing techniques for lithium-ion and sodium-ion batteries.We begin by comparing the unique capabilities of various 3D printing methods against traditional fabrication techniques for producing tailored electrodes.We then address critical challenges across different battery module architectures-cathodes,anodes,electrolytes,and integrated systems-highlighting breakthroughs in material selection,ink formulation,and post-processing.Finally,we explore the future potential of 3Dprinted batteries in next-generation EES devices,emphasizing their role in advancing customizable,high-efficiency solutions.The insights provided herein illuminate how 3D printing can significantly accelerate the development of advanced battery materials,fostering innovation in energy storage technology.
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 Natural Science Foundation of China(22278419)the Key Core Technology Research(Social Development)Foundation of Suzhou(2023ss06)the Suzhou National Joint Laboratory for Green and Low-carbon Wastewater Treatment and Resource Utilization Technology,Suzhou University of Science and Technology(SZLSDT202404).
文摘Fully utilizing renewable biomass energy is important for saving energy,reducing carbon emissions,and mitigating climate change.As the main hydrolysate of cellulose,a primary component of lignocellulose,glucose could be employed as a starting material to prepare some other functional derivatives for improving the value of biomass resources.The isomerization of glucose to produce fructose is an important intermediate process during numerous high-value-added chemical preparations.Therefore,the development of efficient and selective catalysts for glucose isomerization is of great significance.Currently,glucose isomerase catalysts are limited by the harsh conditions required for microbial activity,which restricts further improvements in fructose yield.Additionally,heterogeneous Bronsted-base and Lewis-acid catalysts commonly employed in chemical isomerization methods often lead to the formation of undesirable by-products,resulting in reduced selectivity toward fructose.This study has demonstrated that lithium-loaded heterogeneous catalysts possess excellent isomerization capabilities under mild conditions.A highly efficient Li-C_(3)N_(4) catalyst was developed,achieving a fructose selectivity of 99.9% and a yield of 42.6% at 60℃ within 1.0 h-comparable to the performance of the enzymatic method.Characterization using X-ray photoelectron spectroscopy(XPS),X-ray diffraction(XRD),proton nuclear magnetic resonance(^(1)H NMR),and inductively coupled plasma(ICP)analyses confirmed that lithium was stably incorporated into the g-C_(3)N_(4) framework through the formation of Li-N bonds.Further investigations using CO_(2) temperature-programmed desorption(CO_(2)-TPD),in situ Fourier-transform infrared spectroscopy(FT-IR)and 7Li magic angle spinning nuclear magnetic resonance(^(7)Li MAS NMR)indicated that the isomerization proceeded via a base-catalyzed mechanism.The Li species were found to interact with hydroxyl groups generated through hydrolysis and simultaneously coordinated with nitrogen atoms in the C_(3)N_(4) matrix,resulting in the formation of Li-N_(6)-H_(2)O active sites.These active sites facilitated the deprotonation of glucose to form an enolate intermediate,followed by a proton transfer step that generated fructose.This mechanism not only improved the efficiency of fructose production but also provided valuable insight into the catalytic role of lithium within the isomerization process.
