Flexible electrode design with robust structure and good performance is one of the priorities for flexible batteries to power emerging wearable electronics,and organic cathode materials have become contenders for flex...Flexible electrode design with robust structure and good performance is one of the priorities for flexible batteries to power emerging wearable electronics,and organic cathode materials have become contenders for flexible self-supporting electrodes.However,issues such as easy electrolyte solubility and low intrinsic conductivity contribute to high polarization and rapid capacity decay.Herein,we have designed a flexible self-supporting cathode based on perylene-3,4,9,10-tetracarboxylic dianhydride(PTCDA),interfacial engineering enhanced by polypyrrole(PPy),and carbon nanotubes(CNTs),forming the interconnected and flexible PTCDA/PPy/CNTs using polymerization reaction and vacuum filtration methods,effectively curbing those challenges.When used as the cathode of sodium-ion batteries,PTCDA/PPy/CNTs exhibit excellent rate capability(105.7 mAh g^(−1) at 20 C),outstanding cycling stability(79.4%capacity retention at 5 C after 500 cycles),and remarkable wide temperature application capability(86.5 mAh g^(−1) at−30℃ and 115.4 mAh g^(−1) at 60℃).The sodium storage mechanism was verified to be a reversible oxidation reaction between two Na+ions and carbonyl groups by density functional theory calculations,in situ infrared Fourier transform infrared spectroscopy,and in situ Raman spectroscopy.Surprisingly,the pouch cells based on PTCDA/PPy/CNTs exhibit good mechanical flexibility in various mechanical states.This work inspires more rational designs of flexible and self-supporting organic cathodes,promoting the development of high-performance and wide-temperature adaptable wearable electronic devices.展开更多
Sodium-ion batteries(SIBs)have emerged as promising candidate for large-scale energy storage systems,owing to the abundant natural reserves of sodium,low production costs,and similar electrochemical properties to lith...Sodium-ion batteries(SIBs)have emerged as promising candidate for large-scale energy storage systems,owing to the abundant natural reserves of sodium,low production costs,and similar electrochemical properties to lithium-ion batteries.However,the graphite anodes used in commercial lithium-ion batteries cannot be directly applied to sodium-ion batteries.Among various reported anode materials,hard carbon has attracted extensive attention in SIBs because of its excellent sodium storage capability and cost-effectiveness.In this review,we focus on summarizing the recent advances of coal-based hard carbon anode materials for SIBs.We first introduce the common preparation methods of coal-based hard carbon anode materials.In addition,we overview the effective modification strategies(regulation of oxygen-containing groups,hierarchical pore structures engineering,and heteroatom doping)to boost the sodium storage performance of coal-based hard carbon anode materials.Further research directions of coal-based hard carbon anode materials for SIBs are also proposed.This review is expected to significantly promote the commercial application of coal-based hard carbon anodes.展开更多
Hard carbon(HC)anodes are one of the most promising electrodes for sodium-ion batteries(SIBs)because of their low cost,high reversible specific capacity,and suitable operating voltage.However,the poor fast-charging pr...Hard carbon(HC)anodes are one of the most promising electrodes for sodium-ion batteries(SIBs)because of their low cost,high reversible specific capacity,and suitable operating voltage.However,the poor fast-charging properties of HC limits the broad applicability of SIBs in practical scenarios.This review initially meticulously dissects the underlying sodium storage mechanisms and kinetic behaviors of the HC anode,elucidating the direct correlation with the rate capabilities.Afterward,recent advancements in the field are systematically surveyed,encompassing strategies such as structural modification,interface engineering,morphology regulation,and electrolyte optimization.These methodologies are pivotal in addressing the challenges and unlocking the full potential of HC anodes for high-rate SIB applications.Eventually,by synthesizing the current state-of-theart and delineating prospective research directions.This review aims to promote the development of HC,thereby advancing nextgeneration SIBs with superior energy density,cycle life,high-rate capability,and safety,ultimately facilitating the broader adoption of sodium-based energy storage systems.展开更多
Hard carbon(HC)anodes in sodium-ion batteries(SIBs)are prized for their high capacity,durability,costefficiency,environmental sustainability,and safety.The metallic ash elements in HCs inevitably affect the overall pe...Hard carbon(HC)anodes in sodium-ion batteries(SIBs)are prized for their high capacity,durability,costefficiency,environmental sustainability,and safety.The metallic ash elements in HCs inevitably affect the overall performance of SIBs,however,the unclear role of metallic ash elements during carbonization and the electrochemical sodium storage process presents challenges for advancing HC design concepts.In this review,the traditional role of metallic ash element realized in the past and the deep understanding by a new sight from the view of intrinsic types in precursor matrix are initially introduced.Subsequently,the effect of catalyzing graphitization degree,constructing pore structure,tuning SEI formation and tailoring defects of the HCs regulated by extrinsic factors introduced through experimental conditions in recent years are comprehensively summarized.Additionally,future development prospects and perspectives on the research about metallic ash element in HC are also briefly outlined.It is believed that this review can deliver noteworthy viewpoints by introducing metallic ash elements,for the continued development of adjusting the microstructure of HCs at the nanoscale to actualize highperformance SIBs.展开更多
In the post-lithium-ion battery era,potassium-ion batteries(PIBs)show great potential due to their high energy density and economic competitiveness from abundant potassium resources.In comparison with traditional orga...In the post-lithium-ion battery era,potassium-ion batteries(PIBs)show great potential due to their high energy density and economic competitiveness from abundant potassium resources.In comparison with traditional organic electrolytes,aqueous electrolytes bring lower costs,higher safety,and more environmentally friendly preparation processes for PIBs.Against this background,aqueous PIBs(APIBs)have gradually become a research hotspot in the past few years.Cathodes,a critical component of APIBs,directly affect energy density,safety,and stability.Herein,this review systematically summarizes the research progress of typical APIB cathode materials,some breakthrough investigations of which are highlighted.Meanwhile,material synthesis methods,electrolyte design strategies,electrochemical performance optimization pathways,and electrochemical reaction mechanisms are introduced briefly.Finally,the current challenges and corresponding improvement strategies are proposed to provide a reference for further development.展开更多
The rational design of a 3D scaffold with optimized electrical conductivity,sodiophilicity,and sufficient internal space is crucial for suppressing the growth of Na dendrites and accommodating the large volume changes...The rational design of a 3D scaffold with optimized electrical conductivity,sodiophilicity,and sufficient internal space is crucial for suppressing the growth of Na dendrites and accommodating the large volume changes of Na metal anodes during the plating/stripping process.Nevertheless,the uniform conductivity and sodiophilicity of conventional scaffolds often lead to Na metal deposition on the top of the scaffold,thereby hindering the complete functional capabilities of the scaffold.To tackle this challenge,we developed a novel imprinted dual-gradient 3D network skeleton that boasts gradients in both sodiophilicity and conductivity.Both theoretical and experimental analyses indicate that Na metal prefers to nucleate and deposit dendrite-free from the bottom of the 3D skeleton due to its superior conductivity and sodiophilicity.This dual-gradient design enables the electrode to achieve low nucleation overpotential of 11 mV and sustain stable operation for 1900 h at 1.5 m A cm^(-2) /1.5 mAh cm^(-2) and1000 h at 20 mA cm^(-2) /20 mAh cm^(-2) ,far superior to the gradientless electrode.When paired with Na_(3)V_(2) (PO_(4))_(3) cathode,the full cell retains a capacity of 67.6 mAh g^(-1) after 1000 stable cycles with a capacity retention rate of 82.4%at a rate of 10 C.This advanced skeleton structure design is poised to advance the development of high-energy-density alkali metal batteries.展开更多
Lithium metal batteries(LMBs)are regarded as highly promising high-energy-density battery technology,primarily due to the ultrahigh theoretical capacity(3860 mAh g-1)and low electrochemical redox potential(-3.04 V vs....Lithium metal batteries(LMBs)are regarded as highly promising high-energy-density battery technology,primarily due to the ultrahigh theoretical capacity(3860 mAh g-1)and low electrochemical redox potential(-3.04 V vs.SHE)of the lithium metal anode.Nevertheless,the inherent flammability of conventional electrolytes poses significant safety challenges,inevitably limiting the practical deployment of LMBs.Triethyl phosphate(TEP)-based electrolytes,which endow the merits of low cost,exceptional thermal stability,and intrinsic nonflammability,have attracted considerable attention.In this review,we first introduce the key challenges associated with TEP-based electrolytes in LMBs.We then provide a comprehensive overview of recent progress in the development of TEP-based electrolytes in LMBs.Furthermore,we discuss modification strategies and propose future research directions for optimizing TEP-based electrolytes in LMBs.This review aims to provide valuable insights and guidance for the design of advanced TEP-based electrolytes,thereby facilitating the development of stable and safe LMBs.展开更多
In the post-lithium-ion battery era,calcium-ion batteries(CIBs)are considered a desirable candidate due to their great physicochemical and economic properties.Unfortunately,the lack of high-performance cathode materia...In the post-lithium-ion battery era,calcium-ion batteries(CIBs)are considered a desirable candidate due to their great physicochemical and economic properties.Unfortunately,the lack of high-performance cathode materials has limited the development of CIBs to a large extent.Metal oxides are the most studied CIB cathodes by virtue of their superior electrochemical performance,cost advantages,and scalable synthesis.Among numerous metal oxides,layered vanadium oxides are a popular option because of their unique structural properties and high Ca^(2+)storage capability.Herein,VO2(B)nanofibers,a typical layered vanadium oxide,are synthesized by a simple one-step synthesis method using a commercial precursor.Employing as a CIB cathode,it could deliver high reversible capacities of 97.5 mAh·g^(-1) at 5 A·g^(-1) after 1000 cycles and 74.6 mAh·g^(-1) at 10 A·g^(-1) after 2000 cycles.Moreover,a CIB full battery assembled by perylene-3,4,9,10-tetracarboxylic diimide as an anode and the nanofiber as a cathode achieved a specific capacity of 38.8 mAh·g^(-1) at a current density of 0.5 A·g^(-1) even over 30,000 cycles.This work may provide CIBs with a promising cathode material that can be produced on a large scale and at a low cost.展开更多
Sodium-ion batteries have emerged as promising candidates for next-generation large-scale energy storage systems due to the abundance of sodium resources,low solvation energy,and cost-effectiveness.Among the available...Sodium-ion batteries have emerged as promising candidates for next-generation large-scale energy storage systems due to the abundance of sodium resources,low solvation energy,and cost-effectiveness.Among the available cathode materials,vanadium-based sodium phosphate cathodes are particularly notable for their high operating voltage,excellent thermal stability,and superior cycling performance.However,these materials face significant challenges,including sluggish reaction kinetics,the toxicity of vanadium,and poor electronic conductivity.To overcome these limitations and enhance electrochemical performance,various strategies have been explored.These include morphology regulation via diverse synthesis routes and electronic structure optimization through metal doping,which effectively improve the diffusion of Na+and electrons in vanadium-based phosphate cathodes.This review provides a comprehensive overview of the challenges associated with V-based polyanion cathodes and examines the role of morphology and electronic structure design in enhancing performance.Key vanadium-based phosphate frameworks,such as orthophosphates(Na_(3)V_(2)(PO_(4))_(3)),pyrophosphates(NaVP_(2)O_(7),Na_(2)(VO)P_(2)O_(7),Na_(7)V_(3)(P_(2)O_(7))_(4)),and mixed phosphates(Na_(7)V_(4)(P_(2)O_(7))_(4)PO_(4)),are discussed in detail,highlighting recent advances and insights into their structure-property relationships.The design of cathode material morphology offers an effective approach to optimizing material structures,compositions,porosity,and ion/electron diffusion pathways.Simultaneously,electronic structure tuning through element doping allows for the regulation of band structures,electron distribution,diffusion barriers,and the intrinsic conductivity of phosphate compounds.Addressing the challenges associated with vanadium-based sodium phosphate cathode materials,this study proposes feasible solutions and outlines future research directions toward advancement of high-performance vanadium-based polyanion cathodes.展开更多
O3-type layered transition metal oxide cathodes have attracted considerable attention due to their high sodium storage capacity and straight-forward synthesis process.However,their practical applic-ations are limited ...O3-type layered transition metal oxide cathodes have attracted considerable attention due to their high sodium storage capacity and straight-forward synthesis process.However,their practical applic-ations are limited by irreversible phase transitions,transition metal dissolution,and sluggish Na^(+)diffusion kinetics.Herein,a unique high-entropy oxide(HEO),Na_(0.88)K_(0.02)Ni_(0.24)Li_(0.06)Mg_(0.07)Fe_(0.1)Mn_(0.41)Ti_(0.1)Sn_(0.02)O_(2) is constructed by combining biphasic engineering and dual-site high-entropy doping for stable sodium storage.This synergistic effect significantly improves structural stability,enhances particle integrity,suppresses transition metal dissolution,accelerates electrochemical reaction kinetics,and mitigates electrolyte decomposition during the electrochemical cycling.Therefore,the HEO cathode demonstrates exceptional electrochemical performance,delivering a remarkable rate capability of 74.19 mAh·g^(-1) at 10 C and outstanding cycling stability with 82.68% capacity retention after 1000 cycles.In addition,the practical viability of HEO is confirmed by its outstanding air stability and stable operation of full cells.These findings underscore the potential of synergistic effect of biphasic engineering and dual-site high-entropy doping in developing high-performance cathode materials for sodium-ion batteries.展开更多
Aqueous zinc metal batteries(ZMBs)are one of the most promising grid-scale renewable energy storage batteries.However,the practical application of ZMBs is limited by uncontrollable Zn dendrites and parasitic side reac...Aqueous zinc metal batteries(ZMBs)are one of the most promising grid-scale renewable energy storage batteries.However,the practical application of ZMBs is limited by uncontrollable Zn dendrites and parasitic side reactions at the anode interface.Herein,a unique water-confinement hydrogel electrolyte(TONFC/PAM)was constructed by carboxyl-rich nanocellulose(TONFC)and acid amide-rich polyacrylamide(PAM).The parasitic side reactions were effectively suppressed due to limiting the movement of water in the designed hydrogel electrolyte.Meanwhile,the electrostatic interactions with the electron-rich group(-COOH and-CONH2)established fast Zn2+ion transport channels in the electrolyte,enabling an excellent ionic conductivity(30.23 mS cm^(-1))and horizontal deposition of Zn metal.As a result,the Zn||Zn cells and Zn||Cu cells with TONFC/PAM electrolyte achieve a long cycling life of over 1,400 h at 1 mA cm^(-2)and a high average coulombic efficiency of 99.4%,respectively.More importantly,the Zn||MnO2full cells can stably run for 1,000 cycles with a high capacity(~150 mAh g^(-1))at a current density of 2 A g^(-1).These results show that TONFC/PAM is a suitable hydrogel electrolyte for ZMBs,which presents attractive opportunities for future research on ZMBs.展开更多
Microsized bismuth(Bi)with in-situ constructed three-dimensional(3D)porous network has been considered as a promising anode for high-performance potassium-ion batteries(PIBs).However,the mechanism of the in-situ porou...Microsized bismuth(Bi)with in-situ constructed three-dimensional(3D)porous network has been considered as a promising anode for high-performance potassium-ion batteries(PIBs).However,the mechanism of the in-situ porous evolution of microsized Bi during the charge/discharge process is still mysterious.Herein,various electrolytes are employed to disclose the origin of porous evolution of microsized Bi in PIBs.Experimentally and theoretically,the 3D porous network originates from the uniform interfacial charge distribution on the Bi surface in the linear ether-based electrolyte.In addition,the universality of the interfacial charge distribution mechanism was verified by microsized Sn and Sb.The in-situ constructed 3D porous network of Bi enables a superior potassium storage performance in a wide temperature range from-40 to 40℃.More importantly,the K_(0.9)Mn_(0.7)Ni_(0.3)O_(2)||Bi full cell delivers excellent cycling stability(a high capacity retention of 88.44%even after 2,000 cycles)and good temperature tolerance.This work gives a distinct clarification of the origin of the porous evolution of microsized Bi during cycling,which is critical for developing high-performance PIBs.展开更多
Na_(4)Fe_(3)(PO_(4))_(2)(P_(2)O_(7))(NFPP)with the advantages of low cost and stable crystal structure has been considered a highly promising cathode candidate for sodiumion batteries.However,limited by its undesirabl...Na_(4)Fe_(3)(PO_(4))_(2)(P_(2)O_(7))(NFPP)with the advantages of low cost and stable crystal structure has been considered a highly promising cathode candidate for sodiumion batteries.However,limited by its undesirable intrinsic conductivity,it still suffers from unsatisfactory electrochemical performance.Herein,we synthesized NFPP/C composites with porous structure(p-NFPP)by a facile selfassembly strategy.Its well-developed pore structure can effectively reduce the ion diffusion path,accelerate electrolyte infiltration and accommodate volume expansion during the charge/discharge process.In addition,in-situ X-ray diffraction revealed the superior structural stability of p-NFPP.They enable a high reversible capacity(104.8 mAh g−1),and good rate performance(75.0 mAh g−1 at 10 A g−1),and excellent cycling stability(a reversible capacity of 85.1 mAh g−1 after 2000 cycles).More importantly,the p-NFPP realizes a stable operation in a wide temperature range of 55℃ to−10℃.This work highlights morphology engineering as a powerful strategy to boost the all-climate sodium storage performance of electrode materials.展开更多
基金Shuangqiang Chen gratefully acknowledges the NationalNatural Science Foundation ofChina(21975154,22179078)Zhejiang Provincial Natural Science Founda-tion of China(LY24E020002)+3 种基金Shanghai MunicipalEducation Commission(Innovation Program:2019-01-07-00-09-E00021)the Innovative Research Team of High-level Local Universities in Shanghai.Bing Sunwould like to thank the financial support from ARCthrough the ARC Future Fellowship(FT220100561)YaoXiao would like to thank the financial support from theNatural Science Foundation of Zhejiang Province(LQ23E020002)the Wenzhou Key Scientific andTechnological Innovation Research Project(ZG2023053)
文摘Flexible electrode design with robust structure and good performance is one of the priorities for flexible batteries to power emerging wearable electronics,and organic cathode materials have become contenders for flexible self-supporting electrodes.However,issues such as easy electrolyte solubility and low intrinsic conductivity contribute to high polarization and rapid capacity decay.Herein,we have designed a flexible self-supporting cathode based on perylene-3,4,9,10-tetracarboxylic dianhydride(PTCDA),interfacial engineering enhanced by polypyrrole(PPy),and carbon nanotubes(CNTs),forming the interconnected and flexible PTCDA/PPy/CNTs using polymerization reaction and vacuum filtration methods,effectively curbing those challenges.When used as the cathode of sodium-ion batteries,PTCDA/PPy/CNTs exhibit excellent rate capability(105.7 mAh g^(−1) at 20 C),outstanding cycling stability(79.4%capacity retention at 5 C after 500 cycles),and remarkable wide temperature application capability(86.5 mAh g^(−1) at−30℃ and 115.4 mAh g^(−1) at 60℃).The sodium storage mechanism was verified to be a reversible oxidation reaction between two Na+ions and carbonyl groups by density functional theory calculations,in situ infrared Fourier transform infrared spectroscopy,and in situ Raman spectroscopy.Surprisingly,the pouch cells based on PTCDA/PPy/CNTs exhibit good mechanical flexibility in various mechanical states.This work inspires more rational designs of flexible and self-supporting organic cathodes,promoting the development of high-performance and wide-temperature adaptable wearable electronic devices.
基金supported by the Yunnan Major Scientific and Technological Projects(No.202202AG050003)the National Natural Science Foundation of China(Nos.52262034 and 52202286)+4 种基金the Natural Science Foundation of Yunnan Province(No.202401AW070016)Natural Science Foundation of Zhejiang Province(No.LY24B030006)Key Laboratory of Ionic Rare Earth Resources and Environment,Ministry of Natural Resources of the People’s Republic of China(No.2023IRERE206)Science and Technology Plan Project of Wenzhou Municipality(No.ZG2024055)the Project Funding from“Xingdian Talent Support Plan”.
文摘Sodium-ion batteries(SIBs)have emerged as promising candidate for large-scale energy storage systems,owing to the abundant natural reserves of sodium,low production costs,and similar electrochemical properties to lithium-ion batteries.However,the graphite anodes used in commercial lithium-ion batteries cannot be directly applied to sodium-ion batteries.Among various reported anode materials,hard carbon has attracted extensive attention in SIBs because of its excellent sodium storage capability and cost-effectiveness.In this review,we focus on summarizing the recent advances of coal-based hard carbon anode materials for SIBs.We first introduce the common preparation methods of coal-based hard carbon anode materials.In addition,we overview the effective modification strategies(regulation of oxygen-containing groups,hierarchical pore structures engineering,and heteroatom doping)to boost the sodium storage performance of coal-based hard carbon anode materials.Further research directions of coal-based hard carbon anode materials for SIBs are also proposed.This review is expected to significantly promote the commercial application of coal-based hard carbon anodes.
基金supported by the National Natural Science Foundation of China(52402302,52250710680)the High-end Foreign Experts Recruitment Plan of China(G2023016009L)+4 种基金the Zhejiang Provincial Natural Science Foundation of China(LQ24E020001)the Key Research and Development Program of Zhejiang Province(2023C01232)the Basic Research Project of Wenzhou City(G2023016)the Science and Technology Plan Project of Wenzhou Municipality(ZG2022032)the Natural Science Foundation of Changsha(kq2402017).
文摘Hard carbon(HC)anodes are one of the most promising electrodes for sodium-ion batteries(SIBs)because of their low cost,high reversible specific capacity,and suitable operating voltage.However,the poor fast-charging properties of HC limits the broad applicability of SIBs in practical scenarios.This review initially meticulously dissects the underlying sodium storage mechanisms and kinetic behaviors of the HC anode,elucidating the direct correlation with the rate capabilities.Afterward,recent advancements in the field are systematically surveyed,encompassing strategies such as structural modification,interface engineering,morphology regulation,and electrolyte optimization.These methodologies are pivotal in addressing the challenges and unlocking the full potential of HC anodes for high-rate SIB applications.Eventually,by synthesizing the current state-of-theart and delineating prospective research directions.This review aims to promote the development of HC,thereby advancing nextgeneration SIBs with superior energy density,cycle life,high-rate capability,and safety,ultimately facilitating the broader adoption of sodium-based energy storage systems.
基金supported by the National Natural Science Foundation of China(52402302,52250710680)High-end Foreign Experts Recruitment Plan of China(G2023016009L)+3 种基金Zhejiang Provincial Natural Science Foundation of China(LQ24E020001)Key Research and Development Program of Zhejiang Province(2024C01057,2023C01232)Science and Technology Plan Project of Wenzhou Municipality(ZG2022032)The Natural Science Foundation of Changsha(kq2402017).
文摘Hard carbon(HC)anodes in sodium-ion batteries(SIBs)are prized for their high capacity,durability,costefficiency,environmental sustainability,and safety.The metallic ash elements in HCs inevitably affect the overall performance of SIBs,however,the unclear role of metallic ash elements during carbonization and the electrochemical sodium storage process presents challenges for advancing HC design concepts.In this review,the traditional role of metallic ash element realized in the past and the deep understanding by a new sight from the view of intrinsic types in precursor matrix are initially introduced.Subsequently,the effect of catalyzing graphitization degree,constructing pore structure,tuning SEI formation and tailoring defects of the HCs regulated by extrinsic factors introduced through experimental conditions in recent years are comprehensively summarized.Additionally,future development prospects and perspectives on the research about metallic ash element in HC are also briefly outlined.It is believed that this review can deliver noteworthy viewpoints by introducing metallic ash elements,for the continued development of adjusting the microstructure of HCs at the nanoscale to actualize highperformance SIBs.
基金financially supported by the National Natural Science Foundation of China(52201259,52202286,52002094)the Education Department of Liaoning Province(JYTQN2023285)+5 种基金the Shenyang University of Technology(QNPY202209-4)the Key Laboratory of Functional Inorganic Material Chemistry(Heilongjiang University,Ministry of Education)the Science and Technology Department of Liaoning Province(2024-BSLH-172,JYTMS20231216)the Natural Science Foundation of Zhejiang Province(LY24B030006)the Science and Technology Plan Project of Wenzhou Municipality(ZG2024055)the Shenzhen Science and Technology Innovation Program(RCBS20210706092218040)。
文摘In the post-lithium-ion battery era,potassium-ion batteries(PIBs)show great potential due to their high energy density and economic competitiveness from abundant potassium resources.In comparison with traditional organic electrolytes,aqueous electrolytes bring lower costs,higher safety,and more environmentally friendly preparation processes for PIBs.Against this background,aqueous PIBs(APIBs)have gradually become a research hotspot in the past few years.Cathodes,a critical component of APIBs,directly affect energy density,safety,and stability.Herein,this review systematically summarizes the research progress of typical APIB cathode materials,some breakthrough investigations of which are highlighted.Meanwhile,material synthesis methods,electrolyte design strategies,electrochemical performance optimization pathways,and electrochemical reaction mechanisms are introduced briefly.Finally,the current challenges and corresponding improvement strategies are proposed to provide a reference for further development.
基金supported by the National Natural Science Foundation of China(22209140,52202286)the Qingchuang Technology Support Program of the University in Shandong Province(2024KJH080)+6 种基金the Natural Science Foundation of Shandong Province(ZR2022QE059,ZR2024MB153)the Shandong Laboratory of Advanced Materials and Green Manufacturing at Yantai(Yantai)(AMGM2023A08)the Natural Science Foundation of Zhejiang Province(LQ23B030011,LY24B030006)the Scientific Research Fund of Zhejiang Provincial Education Department(Y202148249)the Science and Technology Plan Project of Wenzhou Municipality(ZG2024055,ZG2022032)the Wenzhou Association for Science and Technology Innovation Program(NLTS2024-013)the Natural Science Foundation of Guangdong Province-Youth Promotion Project(2024A1515030173)。
文摘The rational design of a 3D scaffold with optimized electrical conductivity,sodiophilicity,and sufficient internal space is crucial for suppressing the growth of Na dendrites and accommodating the large volume changes of Na metal anodes during the plating/stripping process.Nevertheless,the uniform conductivity and sodiophilicity of conventional scaffolds often lead to Na metal deposition on the top of the scaffold,thereby hindering the complete functional capabilities of the scaffold.To tackle this challenge,we developed a novel imprinted dual-gradient 3D network skeleton that boasts gradients in both sodiophilicity and conductivity.Both theoretical and experimental analyses indicate that Na metal prefers to nucleate and deposit dendrite-free from the bottom of the 3D skeleton due to its superior conductivity and sodiophilicity.This dual-gradient design enables the electrode to achieve low nucleation overpotential of 11 mV and sustain stable operation for 1900 h at 1.5 m A cm^(-2) /1.5 mAh cm^(-2) and1000 h at 20 mA cm^(-2) /20 mAh cm^(-2) ,far superior to the gradientless electrode.When paired with Na_(3)V_(2) (PO_(4))_(3) cathode,the full cell retains a capacity of 67.6 mAh g^(-1) after 1000 stable cycles with a capacity retention rate of 82.4%at a rate of 10 C.This advanced skeleton structure design is poised to advance the development of high-energy-density alkali metal batteries.
基金supported by the National Natural Science Foundation of China(52202286,22309002,52250710680,52171217)the Key Research and Development Program of Zhejiang Province(2023C01232,2024C01057)+3 种基金the Natural Science Foundation of Zhejiang Province(LY24B030006)the Science and Technology Plan Project of Wenzhou Municipality(ZG2024055,ZG2022032)the Wenzhou Association for Science and Technology Innovation Program(NLTS2024-013)the Basic Research Project of Wenzhou City(G20220016)。
文摘Lithium metal batteries(LMBs)are regarded as highly promising high-energy-density battery technology,primarily due to the ultrahigh theoretical capacity(3860 mAh g-1)and low electrochemical redox potential(-3.04 V vs.SHE)of the lithium metal anode.Nevertheless,the inherent flammability of conventional electrolytes poses significant safety challenges,inevitably limiting the practical deployment of LMBs.Triethyl phosphate(TEP)-based electrolytes,which endow the merits of low cost,exceptional thermal stability,and intrinsic nonflammability,have attracted considerable attention.In this review,we first introduce the key challenges associated with TEP-based electrolytes in LMBs.We then provide a comprehensive overview of recent progress in the development of TEP-based electrolytes in LMBs.Furthermore,we discuss modification strategies and propose future research directions for optimizing TEP-based electrolytes in LMBs.This review aims to provide valuable insights and guidance for the design of advanced TEP-based electrolytes,thereby facilitating the development of stable and safe LMBs.
基金financially supported by the Education Department of Liaoning Province(No.JYTQN2023285)the Shenyang University of Technology(No.QNPY202209-4)+7 种基金the Key Laboratory of Functional Inorganic Material Chemistry(Heilongjiang University,Ministry of Education)the Science and Technology Department of Liaoning Province(No.2024-BSLH-172)the China Scholarship Council(No.202408320117)for the financial supportthe National Natural Science Foundation of China(No.52307243)the Natural Science Foundation of Jiangsu Province(No.BK20230537)the China Postdoctoral Science Foundation(No.2023M741451)the Natural Science Foundation of the Jiangsu Higher Education Institutions of China(No.23KJB140003)the Jiangsu University Advanced Talent Research Startup Fund(No.22JDG052).
文摘In the post-lithium-ion battery era,calcium-ion batteries(CIBs)are considered a desirable candidate due to their great physicochemical and economic properties.Unfortunately,the lack of high-performance cathode materials has limited the development of CIBs to a large extent.Metal oxides are the most studied CIB cathodes by virtue of their superior electrochemical performance,cost advantages,and scalable synthesis.Among numerous metal oxides,layered vanadium oxides are a popular option because of their unique structural properties and high Ca^(2+)storage capability.Herein,VO2(B)nanofibers,a typical layered vanadium oxide,are synthesized by a simple one-step synthesis method using a commercial precursor.Employing as a CIB cathode,it could deliver high reversible capacities of 97.5 mAh·g^(-1) at 5 A·g^(-1) after 1000 cycles and 74.6 mAh·g^(-1) at 10 A·g^(-1) after 2000 cycles.Moreover,a CIB full battery assembled by perylene-3,4,9,10-tetracarboxylic diimide as an anode and the nanofiber as a cathode achieved a specific capacity of 38.8 mAh·g^(-1) at a current density of 0.5 A·g^(-1) even over 30,000 cycles.This work may provide CIBs with a promising cathode material that can be produced on a large scale and at a low cost.
基金supported by the National Natural Science Foundation of China(NSFC)(22105059,22179078,22479115)the Beijing-Tianjin-Hebei Basic Research Cooperation Special Project(B2024204027)+5 种基金the Youth Top-notch Talent Foundation of Hebei Provincial Universities(BJK2022023)the Natural Science Foundation of Hebei Province(B2023204006)the talent training project of Hebei province(No.B20231004)the Innovative Research Team of High-level Local Universities in ShanghaiZhejiang Provincial Natural Science Foundation of China(LY24E020002)Wenzhou basic scientific research project(G20240022)。
文摘Sodium-ion batteries have emerged as promising candidates for next-generation large-scale energy storage systems due to the abundance of sodium resources,low solvation energy,and cost-effectiveness.Among the available cathode materials,vanadium-based sodium phosphate cathodes are particularly notable for their high operating voltage,excellent thermal stability,and superior cycling performance.However,these materials face significant challenges,including sluggish reaction kinetics,the toxicity of vanadium,and poor electronic conductivity.To overcome these limitations and enhance electrochemical performance,various strategies have been explored.These include morphology regulation via diverse synthesis routes and electronic structure optimization through metal doping,which effectively improve the diffusion of Na+and electrons in vanadium-based phosphate cathodes.This review provides a comprehensive overview of the challenges associated with V-based polyanion cathodes and examines the role of morphology and electronic structure design in enhancing performance.Key vanadium-based phosphate frameworks,such as orthophosphates(Na_(3)V_(2)(PO_(4))_(3)),pyrophosphates(NaVP_(2)O_(7),Na_(2)(VO)P_(2)O_(7),Na_(7)V_(3)(P_(2)O_(7))_(4)),and mixed phosphates(Na_(7)V_(4)(P_(2)O_(7))_(4)PO_(4)),are discussed in detail,highlighting recent advances and insights into their structure-property relationships.The design of cathode material morphology offers an effective approach to optimizing material structures,compositions,porosity,and ion/electron diffusion pathways.Simultaneously,electronic structure tuning through element doping allows for the regulation of band structures,electron distribution,diffusion barriers,and the intrinsic conductivity of phosphate compounds.Addressing the challenges associated with vanadium-based sodium phosphate cathode materials,this study proposes feasible solutions and outlines future research directions toward advancement of high-performance vanadium-based polyanion cathodes.
基金funded by the National Natural Science Foundation of China(Nos.22005082,52202286,and 22309002)Project supported by the Young Scientists Fund of the National Natural Science Foundation of China(No.12204143)+9 种基金Science Research Project of Hebei Education Department(Nos.CXY2024036 and QN2024190)Special Project of Local Science and Technology Development Guided by the Central Government of China(Nos.226Z4402G and 246Z4410G)Natural Science Foundation of Zhejiang Province(No.LY24B030006)Science and Technology Plan Project of Wenzhou Municipality(No.ZG2024055)Basic Research Project of Wenzhou City(No.G20220016)Natural Science Foundation of Hebei Province(Nos.B2024202022 and B2024202081)the Tianjin Science and Technology Plan Project(No.24JCQNJC00750)Anhui Provincial Natural Science Foundation(No.2308085QB55)Basic Research Program of Shijiazhuang(No.241790717A)the Postdoctoral Funding Project of Hebei Province(No.B2023003015).
文摘O3-type layered transition metal oxide cathodes have attracted considerable attention due to their high sodium storage capacity and straight-forward synthesis process.However,their practical applic-ations are limited by irreversible phase transitions,transition metal dissolution,and sluggish Na^(+)diffusion kinetics.Herein,a unique high-entropy oxide(HEO),Na_(0.88)K_(0.02)Ni_(0.24)Li_(0.06)Mg_(0.07)Fe_(0.1)Mn_(0.41)Ti_(0.1)Sn_(0.02)O_(2) is constructed by combining biphasic engineering and dual-site high-entropy doping for stable sodium storage.This synergistic effect significantly improves structural stability,enhances particle integrity,suppresses transition metal dissolution,accelerates electrochemical reaction kinetics,and mitigates electrolyte decomposition during the electrochemical cycling.Therefore,the HEO cathode demonstrates exceptional electrochemical performance,delivering a remarkable rate capability of 74.19 mAh·g^(-1) at 10 C and outstanding cycling stability with 82.68% capacity retention after 1000 cycles.In addition,the practical viability of HEO is confirmed by its outstanding air stability and stable operation of full cells.These findings underscore the potential of synergistic effect of biphasic engineering and dual-site high-entropy doping in developing high-performance cathode materials for sodium-ion batteries.
基金supported by the National Natural Science Foundation of China(22209140,52202286)the Natural Science Foundation of Shandong Province(ZR2022QE059)+5 种基金the Shandong Laboratory of Advanced Materials and Green Manufacturing at Yantai(AMGM2023A08)the Natural Science Foundation of Zhejiang Province(LQ23B030011,LY24B030006)the Scientific Research Fund of Zhejiang Provincial Education Department(Y202148249)Science and Technology Plan Project of Wenzhou Municipality(ZG2024055)Wenzhou Association for Science and Technology Innovation Program(NLTS2024-013)the Basic Research Project of Wenzhou City(G20220016)。
文摘Aqueous zinc metal batteries(ZMBs)are one of the most promising grid-scale renewable energy storage batteries.However,the practical application of ZMBs is limited by uncontrollable Zn dendrites and parasitic side reactions at the anode interface.Herein,a unique water-confinement hydrogel electrolyte(TONFC/PAM)was constructed by carboxyl-rich nanocellulose(TONFC)and acid amide-rich polyacrylamide(PAM).The parasitic side reactions were effectively suppressed due to limiting the movement of water in the designed hydrogel electrolyte.Meanwhile,the electrostatic interactions with the electron-rich group(-COOH and-CONH2)established fast Zn2+ion transport channels in the electrolyte,enabling an excellent ionic conductivity(30.23 mS cm^(-1))and horizontal deposition of Zn metal.As a result,the Zn||Zn cells and Zn||Cu cells with TONFC/PAM electrolyte achieve a long cycling life of over 1,400 h at 1 mA cm^(-2)and a high average coulombic efficiency of 99.4%,respectively.More importantly,the Zn||MnO2full cells can stably run for 1,000 cycles with a high capacity(~150 mAh g^(-1))at a current density of 2 A g^(-1).These results show that TONFC/PAM is a suitable hydrogel electrolyte for ZMBs,which presents attractive opportunities for future research on ZMBs.
基金supported by the National Natural Science Foundation of China(No.22005082,52202286)Natural Science Foundation of Hebei Province(No.B2020202065)+2 种基金the Special Project of Local Science and Technology Development Guided by the Central Government of China(226Z4402G)Science Research Project of Hebei Education Department(No.QN2020209,CXY2024036)Basic Research Project of Wenzhou City(G20220016)。
文摘Microsized bismuth(Bi)with in-situ constructed three-dimensional(3D)porous network has been considered as a promising anode for high-performance potassium-ion batteries(PIBs).However,the mechanism of the in-situ porous evolution of microsized Bi during the charge/discharge process is still mysterious.Herein,various electrolytes are employed to disclose the origin of porous evolution of microsized Bi in PIBs.Experimentally and theoretically,the 3D porous network originates from the uniform interfacial charge distribution on the Bi surface in the linear ether-based electrolyte.In addition,the universality of the interfacial charge distribution mechanism was verified by microsized Sn and Sb.The in-situ constructed 3D porous network of Bi enables a superior potassium storage performance in a wide temperature range from-40 to 40℃.More importantly,the K_(0.9)Mn_(0.7)Ni_(0.3)O_(2)||Bi full cell delivers excellent cycling stability(a high capacity retention of 88.44%even after 2,000 cycles)and good temperature tolerance.This work gives a distinct clarification of the origin of the porous evolution of microsized Bi during cycling,which is critical for developing high-performance PIBs.
基金supported by the National Natural Science Foundation of China(52202286,22309002,52250710680,and 52171217)Natural Science Foundation of Zhejiang Province(LY24B030006)+4 种基金High-end Foreign Experts Recruitment Plan of China(G2023016009L)Key Research and Development Program of Zhejiang Province(2023C01232,and 2024C01057)Basic Research Project of Wenzhou City(G20220016)Science and Technology Plan Project of Wenzhou Municipality(ZG2022032)the Faraday Institution NEXGENNA project(FIRG064)for financial support。
文摘Na_(4)Fe_(3)(PO_(4))_(2)(P_(2)O_(7))(NFPP)with the advantages of low cost and stable crystal structure has been considered a highly promising cathode candidate for sodiumion batteries.However,limited by its undesirable intrinsic conductivity,it still suffers from unsatisfactory electrochemical performance.Herein,we synthesized NFPP/C composites with porous structure(p-NFPP)by a facile selfassembly strategy.Its well-developed pore structure can effectively reduce the ion diffusion path,accelerate electrolyte infiltration and accommodate volume expansion during the charge/discharge process.In addition,in-situ X-ray diffraction revealed the superior structural stability of p-NFPP.They enable a high reversible capacity(104.8 mAh g−1),and good rate performance(75.0 mAh g−1 at 10 A g−1),and excellent cycling stability(a reversible capacity of 85.1 mAh g−1 after 2000 cycles).More importantly,the p-NFPP realizes a stable operation in a wide temperature range of 55℃ to−10℃.This work highlights morphology engineering as a powerful strategy to boost the all-climate sodium storage performance of electrode materials.
