Sodium-ion batteries(SIBs)are regarded as the most promising technology for large-scale energy storage systems.However,the practical application of SIBs is still hindered by the lack of applicable cathode materials.He...Sodium-ion batteries(SIBs)are regarded as the most promising technology for large-scale energy storage systems.However,the practical application of SIBs is still hindered by the lack of applicable cathode materials.Herein,a novel phase-pure polyanionic Na_(8)Fe_(5)(SO_(4))_(9) is designed and employed as a cathode material for SIBs for the first time.The Na_(8)Fe_(5)(SO_(4))_(9) has an alluaudite-type sulfate framework and small Naþion diffusion barriers.As expected,the as-synthesized Na_(8)Fe_(5)(SO_(4))_(9)@rGO exhibits a high working potential of 3.8 V(versus Na/Naþ),a superior reversible capacity of 100.2 mAh g1 at 0.2 C,excellent rate performance(~80 mAh g1 at 10 C,~63 mAh g1 at 50 C),and an ultra-long cycling life(91.9%capacity retention after 10,000 cycles at 10 C,81%capacity retention after 20,000 cycles at 50 C).We use various techniques and computational methods to comprehensively investigate the electrochemical reaction mechanisms of Na_(8)Fe_(5)(SO_(4))_(9)@rGO.展开更多
铁基硫酸盐聚阴离子材料因其成本低廉、电化学性能优异等优点,是钠离子电池大规模应用最有前景的候选材料之一.尽管Na_(2)Fe_(2)(SO_(4))_(3),Na_(2)Fe_(1.5)(SO_(4))_(3),Na_(2.4)Fe_(1.8)(SO_(4))_(3)和Na_(2.4)Fe_(1.8)(SO_(4))_(3)...铁基硫酸盐聚阴离子材料因其成本低廉、电化学性能优异等优点,是钠离子电池大规模应用最有前景的候选材料之一.尽管Na_(2)Fe_(2)(SO_(4))_(3),Na_(2)Fe_(1.5)(SO_(4))_(3),Na_(2.4)Fe_(1.8)(SO_(4))_(3)和Na_(2.4)Fe_(1.8)(SO_(4))_(3)等Na_(6-2x)Fe_(x)(SO_(4))_(3)(NFSO-x 1.5≤x≤2.0)材料在储钠方面取得了巨大成果,但这些NFSO-x的相和结构特性仍存在争议,难以实现具有最佳电化学性能的纯相材料.本文通过实验方法和密度泛函理论计算研究了6个具有不同x的NFSO-x样品,以分析其相和结构特性.结果表明在NFSO-x的1.6≤x≤1.7区域存在纯相,部分Na离子倾向于占据Fe位点以形成更稳定的框架.NFSO-1.7在NFSO-x样品中表现出最佳的电化学性能,具有高的放电容量(0.1 C时为104.5 mAh g^(-1),接近其理论容量105 mAh g^(-1))、出色的倍率性能(30 C时为81.5 mAh g^(-1)),并在10,000次循环中具有超长的循环稳定性,容量保持率为72.4%.本研究有助于阐明铁基硫酸盐聚阴离子材料的相和结构特征,以促进其在大规模储能中的应用.展开更多
Prussian blue analogues(PBAs)have gained significant popularity as cathode materials for sodium-ion batteries(SIBs)due to their remarkable features such as high capacity and convenient synthesis.However,PBAs usually s...Prussian blue analogues(PBAs)have gained significant popularity as cathode materials for sodium-ion batteries(SIBs)due to their remarkable features such as high capacity and convenient synthesis.However,PBAs usually suffer from kinetic problems during the electrochemical reactions due to sluggish Na~+diffusion in the large crystals,resulting in low-capacity utilization and inferior rate capability.In this study,we present a facile etching method aiming at activating the sodium storage sites and accelerating the Na~+transport of Na_2NiFe(CN)_6(denoted as NaNiHCF)by precisely controlling its morphologies.A progressive corner passivation phenomenon occurred in NaNiHCF during the etching process,which led to a substantial augmentation of the specific surface area as the morphology transitioned from a standard cube to a dice shape.Notably,by controlling the etching time,the obtained NaNiHCF-3 electrode exhibited boosted electrochemical performance with high reversible capacity of 83.5mAh g~(-1)(98.2%of its theoretical capacity),superior rate capability(71.2 mAh g~(-1)at 10 C),and stable cycling life-span at different temperatures.Both experimental and computational methods reveal the remarkably reversible structural evolution process and improved Na~+diffusion coefficient.We believe that this work can serve as an indispensable reference to tailor the structure of PBAs to obtain improved electrochemical performance.展开更多
基金support from the National Nature Science Foundation of China(Nos.U20A20249,21972108,and 22209125).
文摘Sodium-ion batteries(SIBs)are regarded as the most promising technology for large-scale energy storage systems.However,the practical application of SIBs is still hindered by the lack of applicable cathode materials.Herein,a novel phase-pure polyanionic Na_(8)Fe_(5)(SO_(4))_(9) is designed and employed as a cathode material for SIBs for the first time.The Na_(8)Fe_(5)(SO_(4))_(9) has an alluaudite-type sulfate framework and small Naþion diffusion barriers.As expected,the as-synthesized Na_(8)Fe_(5)(SO_(4))_(9)@rGO exhibits a high working potential of 3.8 V(versus Na/Naþ),a superior reversible capacity of 100.2 mAh g1 at 0.2 C,excellent rate performance(~80 mAh g1 at 10 C,~63 mAh g1 at 50 C),and an ultra-long cycling life(91.9%capacity retention after 10,000 cycles at 10 C,81%capacity retention after 20,000 cycles at 50 C).We use various techniques and computational methods to comprehensively investigate the electrochemical reaction mechanisms of Na_(8)Fe_(5)(SO_(4))_(9)@rGO.
基金supported by the National Natural Science Foundation of China(U20A20249,22209125,and 21972108)the Key Research Program of Hubei Province(2020BAA030)。
文摘铁基硫酸盐聚阴离子材料因其成本低廉、电化学性能优异等优点,是钠离子电池大规模应用最有前景的候选材料之一.尽管Na_(2)Fe_(2)(SO_(4))_(3),Na_(2)Fe_(1.5)(SO_(4))_(3),Na_(2.4)Fe_(1.8)(SO_(4))_(3)和Na_(2.4)Fe_(1.8)(SO_(4))_(3)等Na_(6-2x)Fe_(x)(SO_(4))_(3)(NFSO-x 1.5≤x≤2.0)材料在储钠方面取得了巨大成果,但这些NFSO-x的相和结构特性仍存在争议,难以实现具有最佳电化学性能的纯相材料.本文通过实验方法和密度泛函理论计算研究了6个具有不同x的NFSO-x样品,以分析其相和结构特性.结果表明在NFSO-x的1.6≤x≤1.7区域存在纯相,部分Na离子倾向于占据Fe位点以形成更稳定的框架.NFSO-1.7在NFSO-x样品中表现出最佳的电化学性能,具有高的放电容量(0.1 C时为104.5 mAh g^(-1),接近其理论容量105 mAh g^(-1))、出色的倍率性能(30 C时为81.5 mAh g^(-1)),并在10,000次循环中具有超长的循环稳定性,容量保持率为72.4%.本研究有助于阐明铁基硫酸盐聚阴离子材料的相和结构特征,以促进其在大规模储能中的应用.
基金financially supported from the National Natural Science Foundation of China(U20A20249,21972108,and 22209125)。
文摘Prussian blue analogues(PBAs)have gained significant popularity as cathode materials for sodium-ion batteries(SIBs)due to their remarkable features such as high capacity and convenient synthesis.However,PBAs usually suffer from kinetic problems during the electrochemical reactions due to sluggish Na~+diffusion in the large crystals,resulting in low-capacity utilization and inferior rate capability.In this study,we present a facile etching method aiming at activating the sodium storage sites and accelerating the Na~+transport of Na_2NiFe(CN)_6(denoted as NaNiHCF)by precisely controlling its morphologies.A progressive corner passivation phenomenon occurred in NaNiHCF during the etching process,which led to a substantial augmentation of the specific surface area as the morphology transitioned from a standard cube to a dice shape.Notably,by controlling the etching time,the obtained NaNiHCF-3 electrode exhibited boosted electrochemical performance with high reversible capacity of 83.5mAh g~(-1)(98.2%of its theoretical capacity),superior rate capability(71.2 mAh g~(-1)at 10 C),and stable cycling life-span at different temperatures.Both experimental and computational methods reveal the remarkably reversible structural evolution process and improved Na~+diffusion coefficient.We believe that this work can serve as an indispensable reference to tailor the structure of PBAs to obtain improved electrochemical performance.