Selenium(Se),as an important quasi-metal element,has attracted much attention in the fields of thin-film solar cells,electrocatalysts and energy storage applications,due to its unique physical and chemical properties....Selenium(Se),as an important quasi-metal element,has attracted much attention in the fields of thin-film solar cells,electrocatalysts and energy storage applications,due to its unique physical and chemical properties.However,the electrochemical behavior of Se in different systems from electrolytic cell to battery are complex and not fully understood.In this article,we focus on the electrochemical processes of Se in aqueous solutions,molten salts and ionic liquid electrolytes,as well as the application of Se-containing materials in energy storage.Initially,the electrochemical behaviors of Se-containing species in different systems are comprehensively summarized to understand the complexity of the kinetic processes and guide the Se electrodeposition.Then,the relationship between the deposition conditions and resulting structure and morphology of electrodeposited Se is discussed,so as to regulate the morphology and composition of the products.Finally,the advanced energy storage applications of Se in thin-film solar cells and secondary batteries are reviewed,and the electrochemical reaction processes of Se are systematically comprehended in monovalent and multivalent metal-ion batteries.Based on understanding the fundamental electrochemistry mechanism,the future development directions of Se-containing materials are considered in view of the in-depth review of reaction kinetics and energy storage applications.展开更多
Recycling spent lithium-ion batteries is essential for alleviating resource shortages and environmental pollution,with cathode material recovery being especially significant due to its high content of valuable element...Recycling spent lithium-ion batteries is essential for alleviating resource shortages and environmental pollution,with cathode material recovery being especially significant due to its high content of valuable elements.Relithiation is crucial for the direct regeneration of spent cathodes,and defective structures(Li vacancies,spinel/rock salt)in layered cathodes can only be completely repaired in an environment with adequate Li.However,cathode materials recycled by relithiation suffer the formation of dense spinel/rock salt structure,induced by the migration of transition metals(TMs)to the Li layer and resulting in the creation of TMO_(6)octahedron,which hinders Li^(+)transport between adjacent LiO_(4)tetrahedra,and further greatly impedes the relithiation of the spent cathodes.Here,we regulated lattice stress at the defect structures to break the lattice symmetry of the unfavorable TMO_(6)octahedron and consequently form a quasi LiO_(6)octahedral sites with a low Li^(+)transport energy barrier.This approach ensures a Li-sufficient environment,facilitating the effective relithiation and structural repair of spent cathodes.The combination of theoretical calculations and experimental approaches proves the advantage of symmetry breaking over the traditional relithiation process in repairing the structure of spent cathodes.The proposed repair strategy paves the way for the exploration of more efficient repair methods for spent cathode materials.展开更多
Lithium-sulfur batteries(LSBs)have emerged as one of the most promising next-generation energy storage systems due to their high theoretical energy density(~2600 Wh·kg^(-1))and cost-effectiveness.However,critical...Lithium-sulfur batteries(LSBs)have emerged as one of the most promising next-generation energy storage systems due to their high theoretical energy density(~2600 Wh·kg^(-1))and cost-effectiveness.However,critical challenges,including polysulfide shuttling,lithium dendrite formation,and interfacial instability,persistently hinder their practical implementation.Conventional material design approaches face intrinsic limitations in reconciling structural stability with catalytic efficacy,underscoring the need for innovative solutions.High-entropy materials(HEMs),a novel class of multi-component systems typically comprising five or more principal elements,have recently demonstrated exceptional potential in addressing these challenges through their unique entropy stabilization effect,lattice distortion engineering,and multi-active site synergy.Since the advent of high-entropy alloys(HEAs),this design concept has been successfully extended to oxides,sulfides,nitrides,and electrolyte systems,where it exhibits unparalleled advantages in LSB applications.This review systematically evaluates recent advancements in the engineering of HEMs for sulfur cathodes,lithium metal anodes,and liquid electrolytes,with a focus on elucidating the mechanistic underpinnings of their enhanced ion transport,catalytic conversion,and interfacial stabilization capabilities.By establishing structure-property relationships and delineating performance optimization pathways,this work constructs a robust framework to accelerate the development of HEMs in energy storage systems while highlighting critical challenges and strategic directions for scalable deployment.展开更多
The polysulfide shuttling and sluggish redox kinetics,due to the notorious adsorption-catalysis underperformance,are the ultimate obstacles of the practical application of lithium-sulfur(Li-S)batteries.Conventional ca...The polysulfide shuttling and sluggish redox kinetics,due to the notorious adsorption-catalysis underperformance,are the ultimate obstacles of the practical application of lithium-sulfur(Li-S)batteries.Conventional carbon-based and transition metal compound-based material solutions generally suffer from poor catalysis and adsorption,respectively,despite the performance gain in terms of the other.Herein,we have enhanced polysulfide adsorptioncatalytic capability and protected the Li anode using a complementary bimetallic carbide electrocatalyst,Co3 Mo3 C,modified commercial separator.With this demonstration,the potentials of bimetal compounds,which have been well recognized in other environmental catalysis,are also extended to Li-S batteries.Coupled with this modified separator,a simple cathode(S/Super P composite)can deliver high sulfur utilization,high rate performance,and excellent cycle stability with a low capacity decay rate of^0.034%per cycle at 1 C up to1000 cycles.Even at a high S-loading of 8.0 mg cm^-2 with electrolyte/sulfur ratio=6 m L g^-1,the cathode still exhibits high areal capacity of^6.8 m A h cm^-2.The experimental analysis and the first-principles calculations proved that the bimetallic carbide Co3 Mo3 C provides more binding sites for adsorbing polysulfides and catalyzing the multiphase conversion of sulfur/polysulfide/sulfide than monometallic carbide Mo2 C.Moreover,the modified separator can be reutilized with comparable electrochemical performance.We also showed other bimetallic carbides with similar catalytic effects on Li-S batteries and this material family has great promise indifferent energy electrocatalytic systems.展开更多
Nano Research volume 13,pages2289–2298(2020)Cite this article 347 Accesses 1 Altmetric Metrics details Abstract Sodium-ion batteries(SIBs)are promising power sources due to the low cost and abundance of battery-grade...Nano Research volume 13,pages2289–2298(2020)Cite this article 347 Accesses 1 Altmetric Metrics details Abstract Sodium-ion batteries(SIBs)are promising power sources due to the low cost and abundance of battery-grade sodium resources,while practical SIBs suffer from intrinsically sluggish diffusion kinetics and severe volume changes of electrode materials.Metal-organic framework(MOFs)derived carbonaceous metal compound offer promising applications in electrode materials due to their tailorable composition,nanostructure,chemical and physical properties.Here,we fabricated hierarchical MOF-derived carbonaceous nickel selenides with bi-phase composition for enhanced sodium storage capability.As MOF formation time increases,the pyrolyzed and selenized products gradually transform from a single-phase Ni3Se4 into bi-phase NiSex then single-phase NiSe2,with concomitant morphological evolution from solid spheres into hierarchical urchin-like yolk-shell structures.As SIBs anodes,bi-phase NiSex@C/CNT-10h(10 h of hydrothermal synthesis time)exhibits a high specific capacity of 387.1 mAh/g at 0.1 A/g,long cycling stability of 306.3 mAh/g at a moderately high current density of 1 A/g after 2,000 cycles.Computational simulation further proves the lattice mismatch at the phase boundary facilitates more interstitial space for sodium storage.Our understanding of the phase boundary engineering of transformed MOFs and their morphological evolution is conducive to fabricate novel composites/hybrids for applications in batteries,catalysis,sensors,and environmental remediation.展开更多
Traditional dual-ion lithium salts have been widely used in solid polymer lithium-metal batteries(LMBs).Nevertheless, concentration polarization caused by uncontrolled migration of free anions has severely caused the ...Traditional dual-ion lithium salts have been widely used in solid polymer lithium-metal batteries(LMBs).Nevertheless, concentration polarization caused by uncontrolled migration of free anions has severely caused the growth of lithium dendrites. Although single-ion conductor polymers(SICP) have been developed to reduce concentration polarization, the poor ionic conductivity caused by low carrier concentration limits their application. Herein, a dual-salt quasi-solid polymer electrolyte(QSPE), containing the SICP network as a salt and traditional dual-ion lithium salt, is designed for retarding the movement of free anions and simultaneously providing sufficient effective carriers to alleviate concentration polarization. The dual salt network of this designed QSPE is prepared through in-situ crosslinking copolymerization of SICP monomer, regular ionic conductor, crosslinker with the presence of the dual-ion lithium salt,delivering a high lithium-ion transference number(0.75) and satisfactory ionic conductivity(1.16 × 10^(-3) S cm^(-1) at 30 ℃). Comprehensive characterizations combined with theoretical calculation demonstrate that polyanions from SICP exerts a potential repulsive effect on the transport of free anions to reduce concentration polarization inhibiting lithium dendrites. As a consequence, the Li||LiFePO_4 cell achieves a long-cycle stability for 2000 cycles and a 90% capacity retention at 30 ℃. This work provides a new perspective for reducing concentration polarization and simultaneously enabling enough lithiumions migration for high-performance polymer LMBs.展开更多
基金supported by the Fundamental Research Funds for the Central Universities(FRF-TP-19-079A1)National Natural Science Foundation of China(51804022,51725401)
文摘Selenium(Se),as an important quasi-metal element,has attracted much attention in the fields of thin-film solar cells,electrocatalysts and energy storage applications,due to its unique physical and chemical properties.However,the electrochemical behavior of Se in different systems from electrolytic cell to battery are complex and not fully understood.In this article,we focus on the electrochemical processes of Se in aqueous solutions,molten salts and ionic liquid electrolytes,as well as the application of Se-containing materials in energy storage.Initially,the electrochemical behaviors of Se-containing species in different systems are comprehensively summarized to understand the complexity of the kinetic processes and guide the Se electrodeposition.Then,the relationship between the deposition conditions and resulting structure and morphology of electrodeposited Se is discussed,so as to regulate the morphology and composition of the products.Finally,the advanced energy storage applications of Se in thin-film solar cells and secondary batteries are reviewed,and the electrochemical reaction processes of Se are systematically comprehended in monovalent and multivalent metal-ion batteries.Based on understanding the fundamental electrochemistry mechanism,the future development directions of Se-containing materials are considered in view of the in-depth review of reaction kinetics and energy storage applications.
基金the support from the National Natural Science Foundation of China(22278329,92472124)the High-level Innovation and Entrepreneurship Talent Project of Qinchuangyuan(OCYRCXM-2022-308)+4 种基金the State Key Laboratory for Electrical Insulation and Power Equipment(EIPE23125)the“Young Talent Support Plan”of Xi'an Jiaotong Universitythe Postdoctoral Innovation Talents Support Program(BX20230291)the China Postdoctoral Science Foundation(2024M762607)the Shaanxi Province Postdoctoral Research Funding Program。
文摘Recycling spent lithium-ion batteries is essential for alleviating resource shortages and environmental pollution,with cathode material recovery being especially significant due to its high content of valuable elements.Relithiation is crucial for the direct regeneration of spent cathodes,and defective structures(Li vacancies,spinel/rock salt)in layered cathodes can only be completely repaired in an environment with adequate Li.However,cathode materials recycled by relithiation suffer the formation of dense spinel/rock salt structure,induced by the migration of transition metals(TMs)to the Li layer and resulting in the creation of TMO_(6)octahedron,which hinders Li^(+)transport between adjacent LiO_(4)tetrahedra,and further greatly impedes the relithiation of the spent cathodes.Here,we regulated lattice stress at the defect structures to break the lattice symmetry of the unfavorable TMO_(6)octahedron and consequently form a quasi LiO_(6)octahedral sites with a low Li^(+)transport energy barrier.This approach ensures a Li-sufficient environment,facilitating the effective relithiation and structural repair of spent cathodes.The combination of theoretical calculations and experimental approaches proves the advantage of symmetry breaking over the traditional relithiation process in repairing the structure of spent cathodes.The proposed repair strategy paves the way for the exploration of more efficient repair methods for spent cathode materials.
基金supported by the National Natural Science Foundation of China(No.52402305)the High-level Innovation and Entrepreneurship Talent Project of Qinchuangyuan(No.QCYRCXM-2023-084)+1 种基金the Postdoctoral Fellowship Program of CPSF(Nos.GZB20230570 and 2024M752552)the Natural Science Basic Research Program of Shaanxi(No.2024JC-YBQN-0494)。
文摘Lithium-sulfur batteries(LSBs)have emerged as one of the most promising next-generation energy storage systems due to their high theoretical energy density(~2600 Wh·kg^(-1))and cost-effectiveness.However,critical challenges,including polysulfide shuttling,lithium dendrite formation,and interfacial instability,persistently hinder their practical implementation.Conventional material design approaches face intrinsic limitations in reconciling structural stability with catalytic efficacy,underscoring the need for innovative solutions.High-entropy materials(HEMs),a novel class of multi-component systems typically comprising five or more principal elements,have recently demonstrated exceptional potential in addressing these challenges through their unique entropy stabilization effect,lattice distortion engineering,and multi-active site synergy.Since the advent of high-entropy alloys(HEAs),this design concept has been successfully extended to oxides,sulfides,nitrides,and electrolyte systems,where it exhibits unparalleled advantages in LSB applications.This review systematically evaluates recent advancements in the engineering of HEMs for sulfur cathodes,lithium metal anodes,and liquid electrolytes,with a focus on elucidating the mechanistic underpinnings of their enhanced ion transport,catalytic conversion,and interfacial stabilization capabilities.By establishing structure-property relationships and delineating performance optimization pathways,this work constructs a robust framework to accelerate the development of HEMs in energy storage systems while highlighting critical challenges and strategic directions for scalable deployment.
基金supported by the National Natural Science Foundation of China(21863006,51662029,61974082 and 61704096)Youth Science Foundation of Jiangxi Province(20192BAB216001)Key Laboratory of Jiangxi Province for Environment and Energy Catalysis(20181BCD40004)。
文摘The polysulfide shuttling and sluggish redox kinetics,due to the notorious adsorption-catalysis underperformance,are the ultimate obstacles of the practical application of lithium-sulfur(Li-S)batteries.Conventional carbon-based and transition metal compound-based material solutions generally suffer from poor catalysis and adsorption,respectively,despite the performance gain in terms of the other.Herein,we have enhanced polysulfide adsorptioncatalytic capability and protected the Li anode using a complementary bimetallic carbide electrocatalyst,Co3 Mo3 C,modified commercial separator.With this demonstration,the potentials of bimetal compounds,which have been well recognized in other environmental catalysis,are also extended to Li-S batteries.Coupled with this modified separator,a simple cathode(S/Super P composite)can deliver high sulfur utilization,high rate performance,and excellent cycle stability with a low capacity decay rate of^0.034%per cycle at 1 C up to1000 cycles.Even at a high S-loading of 8.0 mg cm^-2 with electrolyte/sulfur ratio=6 m L g^-1,the cathode still exhibits high areal capacity of^6.8 m A h cm^-2.The experimental analysis and the first-principles calculations proved that the bimetallic carbide Co3 Mo3 C provides more binding sites for adsorbing polysulfides and catalyzing the multiphase conversion of sulfur/polysulfide/sulfide than monometallic carbide Mo2 C.Moreover,the modified separator can be reutilized with comparable electrochemical performance.We also showed other bimetallic carbides with similar catalytic effects on Li-S batteries and this material family has great promise indifferent energy electrocatalytic systems.
基金This research was supported by the National Natural Science Foundation of China(No.51773165)Project of National Defense Science and Technology Innovation Special Zone(No.JZ-20171102)+3 种基金Shaanxi Post-doctoral Foundation(No.2016BSHYDZZ20)Key Laboratory Construction Program of Xi’an Municipal Bureau of Science and Technology(No.201805056ZD7CG40)Innovation Capability Support Program of Shaanxi(No.2018PT-28,2019PT-05)The numerical calculations in this paper have been done on the supercomputing system in the Supercomputing Center of Wuhan University.A.K.C.thanks the Ras al Khaimah Centre for Advanced Materials for financial support.J.H.thanks the financial support(No.DE190100803)。
文摘Nano Research volume 13,pages2289–2298(2020)Cite this article 347 Accesses 1 Altmetric Metrics details Abstract Sodium-ion batteries(SIBs)are promising power sources due to the low cost and abundance of battery-grade sodium resources,while practical SIBs suffer from intrinsically sluggish diffusion kinetics and severe volume changes of electrode materials.Metal-organic framework(MOFs)derived carbonaceous metal compound offer promising applications in electrode materials due to their tailorable composition,nanostructure,chemical and physical properties.Here,we fabricated hierarchical MOF-derived carbonaceous nickel selenides with bi-phase composition for enhanced sodium storage capability.As MOF formation time increases,the pyrolyzed and selenized products gradually transform from a single-phase Ni3Se4 into bi-phase NiSex then single-phase NiSe2,with concomitant morphological evolution from solid spheres into hierarchical urchin-like yolk-shell structures.As SIBs anodes,bi-phase NiSex@C/CNT-10h(10 h of hydrothermal synthesis time)exhibits a high specific capacity of 387.1 mAh/g at 0.1 A/g,long cycling stability of 306.3 mAh/g at a moderately high current density of 1 A/g after 2,000 cycles.Computational simulation further proves the lattice mismatch at the phase boundary facilitates more interstitial space for sodium storage.Our understanding of the phase boundary engineering of transformed MOFs and their morphological evolution is conducive to fabricate novel composites/hybrids for applications in batteries,catalysis,sensors,and environmental remediation.
基金supported by the National Natural Science Foundation of China (52273081 and 22278329)the Natural Science Basic Research Program of Shaanxi (2022TD-27 and 2020-JC-09)+2 种基金Qin Chuangyuan Talent Project of Shaanxi Province (OCYRCXM2022-308)the State Key Laboratory for Electrical Insulation and Power Equipment (EIPE23125)the “Young Talent Support Plan” of Xi’an Jiaotong University。
文摘Traditional dual-ion lithium salts have been widely used in solid polymer lithium-metal batteries(LMBs).Nevertheless, concentration polarization caused by uncontrolled migration of free anions has severely caused the growth of lithium dendrites. Although single-ion conductor polymers(SICP) have been developed to reduce concentration polarization, the poor ionic conductivity caused by low carrier concentration limits their application. Herein, a dual-salt quasi-solid polymer electrolyte(QSPE), containing the SICP network as a salt and traditional dual-ion lithium salt, is designed for retarding the movement of free anions and simultaneously providing sufficient effective carriers to alleviate concentration polarization. The dual salt network of this designed QSPE is prepared through in-situ crosslinking copolymerization of SICP monomer, regular ionic conductor, crosslinker with the presence of the dual-ion lithium salt,delivering a high lithium-ion transference number(0.75) and satisfactory ionic conductivity(1.16 × 10^(-3) S cm^(-1) at 30 ℃). Comprehensive characterizations combined with theoretical calculation demonstrate that polyanions from SICP exerts a potential repulsive effect on the transport of free anions to reduce concentration polarization inhibiting lithium dendrites. As a consequence, the Li||LiFePO_4 cell achieves a long-cycle stability for 2000 cycles and a 90% capacity retention at 30 ℃. This work provides a new perspective for reducing concentration polarization and simultaneously enabling enough lithiumions migration for high-performance polymer LMBs.
