The development of reliable and affordable all-solid-state sodium metal batteries(ASS-SMBs)requires suitable solid-state electrolytes with cost-efficient processing and stabilized electrode/electrolyte interfaces.Here...The development of reliable and affordable all-solid-state sodium metal batteries(ASS-SMBs)requires suitable solid-state electrolytes with cost-efficient processing and stabilized electrode/electrolyte interfaces.Here,an integrated porous/dense/porous Na_(5)YSi_(4)O_(12)(NYS)trilayered scaffold is designed and fabricated by tape casting using aqueous slurries.In this template-based NYS scaffold,the dense layer in the middle serves as a separator and the porous layers on both sides accommodate the active materials with their volume changes during the charge/discharge processes,increasing the contact area and thus enhancing the utilization rate and homogenizing the current distribution.The Na/NYS/Na symmetric cells with the Pb-coated NYS scaffold exhibit significantly reduced interfacial impedance and superior critical current density of up to 3.0 mA cm^(-2)against Na metal owing to enhanced wettability.Furthermore,the assembled Na/NYS/S full cells operated without external pressure at room temperature showed a high initial discharge capacity of 970 mAh g^(-1)and good cycling stability with a capacity of 600 mAh g^(-1)after 150 cycles(based on the mass of sulfur).This approach paves the way for the realization of economical and practical ASS-SMBs from the perspective of ceramic manufacturing.展开更多
Developing cost-effective and reliable solid-state sodium batteries with superior performance is crucial for stationary energy storage.A key component in facilitating their application is a solid-state electrolyte wit...Developing cost-effective and reliable solid-state sodium batteries with superior performance is crucial for stationary energy storage.A key component in facilitating their application is a solid-state electrolyte with high conductivity and stability.Herein,we employed aliovalent cation substitution to enhance ionic conductivity while preserving the crystal structure.Optimized substitution of Y^(3+)with Zr^(4+)in Na_(5)YSi_(4)O_(12) introduced Naþion vacancies,resulting in high bulk and total conductivities of up to 6.5 and 3.3 mS cm^(-1),respectively,at room temperature with the composition Na_(4.92)Y_(0.92)Zr_(0.08)Si_(4)O_(12)(NYZS).NYZS shows exceptional electrochemical stability(up to 10 V vs.Naþ/Na),favorable interfacial compatibility with Na,and an excellent critical current density of 2.4 mA cm^(-2).The enhanced conductivity of Naþions in NYZS was elucidated using solid-state nuclear magnetic resonance techniques and theoretical simulations,revealing two migration routes facilitated by the synergistic effect of increased Naþion vacancies and improved chemical environment due to Zr^(4+)substitution.NYZS extends the list of suitable solid-state electrolytes and enables the facile synthesis of stable,low-cost Naþion silicate electrolytes.展开更多
钠金属二次电池由于丰富的地壳钠资源储备、金属钠负极高的理论容量等优势受到广泛的关注,已成为后锂离子电池时代的重要技术之一.然而,金属钠负极在充放电循环过程中存在枝晶生长、体积变化等严重问题,严重制约了钠金属电池技术的发展...钠金属二次电池由于丰富的地壳钠资源储备、金属钠负极高的理论容量等优势受到广泛的关注,已成为后锂离子电池时代的重要技术之一.然而,金属钠负极在充放电循环过程中存在枝晶生长、体积变化等严重问题,严重制约了钠金属电池技术的发展.基于以上问题,本文提出在金属钠负极体相内引入NaSICON型固态钠离子导体,构建具有离子/电子混合传输能力的金属钠基复合负极.一方面,通过钠离子传导相和金属电子导电相之间的紧密接触构建了快速的离子/电子通道和丰富的电化学反应界面,有利于实现稳定可逆的钠沉积/剥离;另一方面,紧密堆积的复合结构保护了金属钠免受液态有机电解质的腐蚀和副反应的发生.得益于上述独特的结构设计,复合负极表现出高度可逆和稳定的钠的沉积/剥离行为.在碳酸酯类电解液中,对称电池在1 m A cm^(-2)的电流密度、5 m Ah cm^(-2)的高充放电容量下实现了高于700 h的超长寿命,以及高达8 m A cm^(-2)电流密度的出色倍率性能.在搭配Na_(3)V_(2)(PO_(4))_(3)/C正极时,全电池展现出优异的循环稳定性(容量衰减单次平均仅0.012%)以及低的充放电极化.展开更多
基金the China Scholarship Council(CSC,No.201906200023)the MatKat Foundation.Aikai Yang,whose CSC grant application is affiliated with Nankai University(Tianjin,China)the Key Laboratory of Advanced Energy Materials Chemistry(Ministry of Education)at Nankai University.Partial financial support from the German Federal Ministry of Education and Research(BMBF)within the project“HeNa”(support code 13XP0390B)is also gratefully acknowledged.
文摘The development of reliable and affordable all-solid-state sodium metal batteries(ASS-SMBs)requires suitable solid-state electrolytes with cost-efficient processing and stabilized electrode/electrolyte interfaces.Here,an integrated porous/dense/porous Na_(5)YSi_(4)O_(12)(NYS)trilayered scaffold is designed and fabricated by tape casting using aqueous slurries.In this template-based NYS scaffold,the dense layer in the middle serves as a separator and the porous layers on both sides accommodate the active materials with their volume changes during the charge/discharge processes,increasing the contact area and thus enhancing the utilization rate and homogenizing the current distribution.The Na/NYS/Na symmetric cells with the Pb-coated NYS scaffold exhibit significantly reduced interfacial impedance and superior critical current density of up to 3.0 mA cm^(-2)against Na metal owing to enhanced wettability.Furthermore,the assembled Na/NYS/S full cells operated without external pressure at room temperature showed a high initial discharge capacity of 970 mAh g^(-1)and good cycling stability with a capacity of 600 mAh g^(-1)after 150 cycles(based on the mass of sulfur).This approach paves the way for the realization of economical and practical ASS-SMBs from the perspective of ceramic manufacturing.
基金the China Scholarship Council (CSC,Grant Nos.201906200023,201906200016 and 201808080137,respectively)for financial supportfunding from the European Union's Horizon 2020 research,innovation program under the Marie Sklodowska-Curie grant agreement (No.101034329)the WINNING Normandy Program supported by the Normandy Region,France.
文摘Developing cost-effective and reliable solid-state sodium batteries with superior performance is crucial for stationary energy storage.A key component in facilitating their application is a solid-state electrolyte with high conductivity and stability.Herein,we employed aliovalent cation substitution to enhance ionic conductivity while preserving the crystal structure.Optimized substitution of Y^(3+)with Zr^(4+)in Na_(5)YSi_(4)O_(12) introduced Naþion vacancies,resulting in high bulk and total conductivities of up to 6.5 and 3.3 mS cm^(-1),respectively,at room temperature with the composition Na_(4.92)Y_(0.92)Zr_(0.08)Si_(4)O_(12)(NYZS).NYZS shows exceptional electrochemical stability(up to 10 V vs.Naþ/Na),favorable interfacial compatibility with Na,and an excellent critical current density of 2.4 mA cm^(-2).The enhanced conductivity of Naþions in NYZS was elucidated using solid-state nuclear magnetic resonance techniques and theoretical simulations,revealing two migration routes facilitated by the synergistic effect of increased Naþion vacancies and improved chemical environment due to Zr^(4+)substitution.NYZS extends the list of suitable solid-state electrolytes and enables the facile synthesis of stable,low-cost Naþion silicate electrolytes.
基金supported by the National Natural Science Foundation of China(51722105)National Key Research and Development Program(2016YFB0901600)+1 种基金Zhejiang Provincial Natural Science Foundation(LR18B030001)Ten Thousand Talent Program of Zhejiang Province。
文摘钠金属二次电池由于丰富的地壳钠资源储备、金属钠负极高的理论容量等优势受到广泛的关注,已成为后锂离子电池时代的重要技术之一.然而,金属钠负极在充放电循环过程中存在枝晶生长、体积变化等严重问题,严重制约了钠金属电池技术的发展.基于以上问题,本文提出在金属钠负极体相内引入NaSICON型固态钠离子导体,构建具有离子/电子混合传输能力的金属钠基复合负极.一方面,通过钠离子传导相和金属电子导电相之间的紧密接触构建了快速的离子/电子通道和丰富的电化学反应界面,有利于实现稳定可逆的钠沉积/剥离;另一方面,紧密堆积的复合结构保护了金属钠免受液态有机电解质的腐蚀和副反应的发生.得益于上述独特的结构设计,复合负极表现出高度可逆和稳定的钠的沉积/剥离行为.在碳酸酯类电解液中,对称电池在1 m A cm^(-2)的电流密度、5 m Ah cm^(-2)的高充放电容量下实现了高于700 h的超长寿命,以及高达8 m A cm^(-2)电流密度的出色倍率性能.在搭配Na_(3)V_(2)(PO_(4))_(3)/C正极时,全电池展现出优异的循环稳定性(容量衰减单次平均仅0.012%)以及低的充放电极化.
