Solid-state electrolytes are critical for the development of next-generation high-energy and high-safety rechargeable batteries.Among all the candidates,sodium(Na)superionic conductors(NASICONs)are highly promising be...Solid-state electrolytes are critical for the development of next-generation high-energy and high-safety rechargeable batteries.Among all the candidates,sodium(Na)superionic conductors(NASICONs)are highly promising because of their evident advantages in high ionic conductivity and high chemical/electrochemical stability.The concept of NASICONs was proposed by Hong and Goodenough et al.in 1976 by reporting the synthesis and characterization of Na1+xZr2(SixP3−x)O12(0≤x≤3),which has attracted tremendous attention on the NASICONs-type solid-state electrolytes.In this review,we are committed to describing the development history of NASICONs-type solid-state electrolytes and elucidating the contribution of Goodenough as a tribute to him.We summarize the correlations and differences between lithium-based and sodium-based NASICONs electrolytes,such as their preparation methods,structures,ionic conductivities,and the mechanisms of ion transportation.Critical challenges of NASICONs-structured electrolytes are discussed,and several research directions are proposed to tackle the obstacles toward practical applications.展开更多
Sodium-ion batteries(SIBs)have developed rapidly owing to the high natural abundance,wide distribution,and low cost of sodium.Among the various materials used in SIBs,sodium superion conductor(NASICON)-based electrode...Sodium-ion batteries(SIBs)have developed rapidly owing to the high natural abundance,wide distribution,and low cost of sodium.Among the various materials used in SIBs,sodium superion conductor(NASICON)-based electrode materials with remarkable structural stability and high ionic conductivity are one of the most promising candidates for sodium storage electrodes.Nevertheless,the relatively low electronic conductivity of these materials makes them display poor electrochemical performance,significantly limiting their practical application.In recent years,the strategies of enhancing the inherent conductivity of NASICON-based cathode materials have been extensively studied through coating the active material with a conductive carbon layer,reducing the size of the cathode material,combining the cathode material with various carbon materials,and doping elements in the bulk phase.In this paper,we review the recent progress in the development of NASICON-based cathode materials for SIBs in terms of their synthesis,characterization,functional mechanisms,and performance validation/optimization.The advantages and disadvantages of such SIB cathode materials are analyzed,and the relationship between electrode structures and electrochemical performance as well as the strategies for enhancing their electrical conductivity and structural stability is highlighted.Some technical challenges of NASICON-based cathode materials with respect to SIB performance are analyzed,and several future research directions are also proposed for overcoming the challenges toward practical applications.展开更多
Sodium superionic conductors(NASICONs)have attracted enormous attention owing to their excellent ionic diffusion and structural stability.However,the high cost of vanadium,limited capacity due to fewer redox reactions...Sodium superionic conductors(NASICONs)have attracted enormous attention owing to their excellent ionic diffusion and structural stability.However,the high cost of vanadium,limited capacity due to fewer redox reactions,and low electronic conductivity restrict their practical application.Herein,we designed Na_(3.5)V_(0.5)Mn_(0.5)Fe_(0.5)Ti_(0.5)(PO_(4))3 (NVMFTP)medium entropy NASICON with multi-electron reactions as a fast sodium storage cathode for sodium-ion batteries(SIBs).The incorporation of Fe,Mn and Ti not only reduces the cost but also activates multi-redox reactions of V^(2+)/V^(3+),Ti^(3+)/Ti^(4+),Fe^(2+)/Fe^(3+),V^(3+)/V^(4+),Mn^(2+)/Mn^(3+),V^(4+)/V^(5+).Owing to distinctive structural design with medium entropy,the NVMFTP delivered 168 mAh·g^(−1) at 0.5C with a remarkable rate capability of 93.51 mAh·g^(−1) at 60C and steady long-term cycling performance till 5000 cycles.More importantly,NVMFTP takes only 11 min to achieve 80%SOC at 5C.The in-situ and ex-situ X-ray diffraction(XRD)further demonstrate reversible multi-electron reaction mechanisms of slow charging and fast charging.NVMFTP/HC full cell shows 110 mAh·g^(−1) capacity and 208 Wh·kg^(−1) energy density.This study will provide comprehensive insight into developing low-cost,cutting-edge materials for SIBs.展开更多
Compared to traditional liquid electrolyte batteries,solid metal batteries offer advantages such as a wide operating temperature range,high energy density,and improved safety,making them a promising energy storage tec...Compared to traditional liquid electrolyte batteries,solid metal batteries offer advantages such as a wide operating temperature range,high energy density,and improved safety,making them a promising energy storage technology.Solid electrolytes,as the core components of solid‐state batteries,are key factors in advancing solid‐state battery technology.Among various solid electrolytes,Na super ionic conductor(NASICON)‐type solid electrolytes exhibit high ionic conductivity(10−3 S·cm−1),a wide electrochemical window,and good thermal stability,providing room for the development of high energy‐density solid metal batteries.Since the discovery of NASICON‐type solid electrolytes in 1976,interest in their use in all‐solid‐state battery development has grown significantly.In this review,we comprehensively analyze the common features of NASICON lithium‐ion conductors and NASICON sodium‐ion conductors,review the historical development of NASICON‐type solid electrolytes,systematically summarize the transport mechanisms of metal cations in NASICON‐type solid electrolytes,discuss the latest strategies for enhancing ionic conductivity,elaborate on the latest methods for improving mechanical stability and interface stability,and point out the requirements of high energy density devices for NASICON‐type solid electrolytes as well as three types of in situ characterization techniques for interfaces.Finally,we highlight the challenges and potential solutions for the future development of NASICON‐type solid electrolytes and solid‐state metal batteries.展开更多
Sodium-ion batteries are promising candidates for next-generation large-scale energy storage owing to their abundance and low cost.Biphasic intercalation reactions,constrained by kinetic limitations and structural ins...Sodium-ion batteries are promising candidates for next-generation large-scale energy storage owing to their abundance and low cost.Biphasic intercalation reactions,constrained by kinetic limitations and structural instability,fundamentally restrict the rate capability and cycle life of sodium ion batteries.However,precise regulation of these reactions to enhance kinetics remains challenging.Here,we propose a strategy of atomic-scale phase engineering to activate the metastable state and achieve a three-phase reaction through precise Mg^(2+)doping at V sites in Na_(3)V_(2)(PO_(4))_(3).The Mg^(2+)occupancy promotes the exchange between Na1 and Na2 sites,thereby stabilizing a Na_(2)V_(2)(PO_(4))_(3) intermediate.First-principles calculations indicate that Mg^(2+)occupation facilitates charge redistribution by weakening Na-O electrostatic interaction,stabilizing the formation of Na_(2)V_(2)(PO_(4))_(3)phase.The optimized cathode exhibits ultrahigh capacity retention(84.5%after 5000 cycles at 3.51 A g^(-1)),supports ultrafast charging within 120 s,and exceptional rate capability(96.2 mAh g^(-1)at 4.68 A g^(-1)).This work establishes a universal route to unlock hidden reaction pathways by redefining the role of dopants in phase transition control.展开更多
基金National Key Research and Development Program of China,Grant/Award Number:2020YFA0715000National Natural Science Foundation of China,Grant/Award Numbers:51902238,52127816,52172234Fundamental Research Funds for the Central Universities,Grant/Award Numbers:WUT:2020IVA069,2020IVB043,2021IVA020B。
文摘Solid-state electrolytes are critical for the development of next-generation high-energy and high-safety rechargeable batteries.Among all the candidates,sodium(Na)superionic conductors(NASICONs)are highly promising because of their evident advantages in high ionic conductivity and high chemical/electrochemical stability.The concept of NASICONs was proposed by Hong and Goodenough et al.in 1976 by reporting the synthesis and characterization of Na1+xZr2(SixP3−x)O12(0≤x≤3),which has attracted tremendous attention on the NASICONs-type solid-state electrolytes.In this review,we are committed to describing the development history of NASICONs-type solid-state electrolytes and elucidating the contribution of Goodenough as a tribute to him.We summarize the correlations and differences between lithium-based and sodium-based NASICONs electrolytes,such as their preparation methods,structures,ionic conductivities,and the mechanisms of ion transportation.Critical challenges of NASICONs-structured electrolytes are discussed,and several research directions are proposed to tackle the obstacles toward practical applications.
基金the National Natural Science Foundation of China(Nos.51602193,21601122,21905169)the Belt and Road Initiatives International Cooperation Project(No.20640770300)+5 种基金the Shanghai“Chen Guang”Project(16CG63)the Shanghai Local Universities Capacity Building Project of Science and Technology Innovation Action Program(21010501700)the Shanghai Sailing Program(No.18YF1408600)the Fundamental Research Funds for the Central Universities(WD1817002)the EPSRC(EP/R023581/1,EP/P009050/1,EP/V027433/1)the Royal Society(RGS/R1/211080).
文摘Sodium-ion batteries(SIBs)have developed rapidly owing to the high natural abundance,wide distribution,and low cost of sodium.Among the various materials used in SIBs,sodium superion conductor(NASICON)-based electrode materials with remarkable structural stability and high ionic conductivity are one of the most promising candidates for sodium storage electrodes.Nevertheless,the relatively low electronic conductivity of these materials makes them display poor electrochemical performance,significantly limiting their practical application.In recent years,the strategies of enhancing the inherent conductivity of NASICON-based cathode materials have been extensively studied through coating the active material with a conductive carbon layer,reducing the size of the cathode material,combining the cathode material with various carbon materials,and doping elements in the bulk phase.In this paper,we review the recent progress in the development of NASICON-based cathode materials for SIBs in terms of their synthesis,characterization,functional mechanisms,and performance validation/optimization.The advantages and disadvantages of such SIB cathode materials are analyzed,and the relationship between electrode structures and electrochemical performance as well as the strategies for enhancing their electrical conductivity and structural stability is highlighted.Some technical challenges of NASICON-based cathode materials with respect to SIB performance are analyzed,and several future research directions are also proposed for overcoming the challenges toward practical applications.
基金supported by the National Natural Science Foundation of China(Nos.52027801 and 92263203)the National Key R&D Program of China(Nos.2022YFA1203902 and 2022YFA1200093)and the China-Germany Collaboration Project(No.M-0199)。
文摘Sodium superionic conductors(NASICONs)have attracted enormous attention owing to their excellent ionic diffusion and structural stability.However,the high cost of vanadium,limited capacity due to fewer redox reactions,and low electronic conductivity restrict their practical application.Herein,we designed Na_(3.5)V_(0.5)Mn_(0.5)Fe_(0.5)Ti_(0.5)(PO_(4))3 (NVMFTP)medium entropy NASICON with multi-electron reactions as a fast sodium storage cathode for sodium-ion batteries(SIBs).The incorporation of Fe,Mn and Ti not only reduces the cost but also activates multi-redox reactions of V^(2+)/V^(3+),Ti^(3+)/Ti^(4+),Fe^(2+)/Fe^(3+),V^(3+)/V^(4+),Mn^(2+)/Mn^(3+),V^(4+)/V^(5+).Owing to distinctive structural design with medium entropy,the NVMFTP delivered 168 mAh·g^(−1) at 0.5C with a remarkable rate capability of 93.51 mAh·g^(−1) at 60C and steady long-term cycling performance till 5000 cycles.More importantly,NVMFTP takes only 11 min to achieve 80%SOC at 5C.The in-situ and ex-situ X-ray diffraction(XRD)further demonstrate reversible multi-electron reaction mechanisms of slow charging and fast charging.NVMFTP/HC full cell shows 110 mAh·g^(−1) capacity and 208 Wh·kg^(−1) energy density.This study will provide comprehensive insight into developing low-cost,cutting-edge materials for SIBs.
基金supported by the National Natural Science Foundation of China(No.52472137)the Talent Introduction Research Project of Hebei University(No.521100224231)the Shanghai Magnolia Talent Plan Pujiang Project(23PJ1415600)。
文摘Compared to traditional liquid electrolyte batteries,solid metal batteries offer advantages such as a wide operating temperature range,high energy density,and improved safety,making them a promising energy storage technology.Solid electrolytes,as the core components of solid‐state batteries,are key factors in advancing solid‐state battery technology.Among various solid electrolytes,Na super ionic conductor(NASICON)‐type solid electrolytes exhibit high ionic conductivity(10−3 S·cm−1),a wide electrochemical window,and good thermal stability,providing room for the development of high energy‐density solid metal batteries.Since the discovery of NASICON‐type solid electrolytes in 1976,interest in their use in all‐solid‐state battery development has grown significantly.In this review,we comprehensively analyze the common features of NASICON lithium‐ion conductors and NASICON sodium‐ion conductors,review the historical development of NASICON‐type solid electrolytes,systematically summarize the transport mechanisms of metal cations in NASICON‐type solid electrolytes,discuss the latest strategies for enhancing ionic conductivity,elaborate on the latest methods for improving mechanical stability and interface stability,and point out the requirements of high energy density devices for NASICON‐type solid electrolytes as well as three types of in situ characterization techniques for interfaces.Finally,we highlight the challenges and potential solutions for the future development of NASICON‐type solid electrolytes and solid‐state metal batteries.
基金finally supported by the National Natural Science Foundation of China(NSFC Grants 52074098)the Major Science and Technology R&D Special Project in Jiangxi Province(104 Ah high specific energy and fast charging function lithium-ion battery system development and application project 20233AAE02009)the Cospowers Technology Co.,Ltd.,Technology Project Funding(research on key materials and battery technologies for sodium ion batteries,KYDY2022003)。
文摘Sodium-ion batteries are promising candidates for next-generation large-scale energy storage owing to their abundance and low cost.Biphasic intercalation reactions,constrained by kinetic limitations and structural instability,fundamentally restrict the rate capability and cycle life of sodium ion batteries.However,precise regulation of these reactions to enhance kinetics remains challenging.Here,we propose a strategy of atomic-scale phase engineering to activate the metastable state and achieve a three-phase reaction through precise Mg^(2+)doping at V sites in Na_(3)V_(2)(PO_(4))_(3).The Mg^(2+)occupancy promotes the exchange between Na1 and Na2 sites,thereby stabilizing a Na_(2)V_(2)(PO_(4))_(3) intermediate.First-principles calculations indicate that Mg^(2+)occupation facilitates charge redistribution by weakening Na-O electrostatic interaction,stabilizing the formation of Na_(2)V_(2)(PO_(4))_(3)phase.The optimized cathode exhibits ultrahigh capacity retention(84.5%after 5000 cycles at 3.51 A g^(-1)),supports ultrafast charging within 120 s,and exceptional rate capability(96.2 mAh g^(-1)at 4.68 A g^(-1)).This work establishes a universal route to unlock hidden reaction pathways by redefining the role of dopants in phase transition control.
