Na_(3)V_(2)(PO_(4))_(3)(NVP)is gifted with fast Na^(+)conductive NASICON structure.But it still suffers from low electronic conductivity and inadequate energy density.Herein,a high-entropy modification strategy is rea...Na_(3)V_(2)(PO_(4))_(3)(NVP)is gifted with fast Na^(+)conductive NASICON structure.But it still suffers from low electronic conductivity and inadequate energy density.Herein,a high-entropy modification strategy is realized by doping V^(3+)site with Ga^(3+)/Cr^(3+)/Al^(3+)/Fe^(3+)/In^(3+)simultaneously(i.e.Na_(3)V_(2-x)(GaCrAlFeIn)_x(PO_(4))_(3);x=0,0.04,0.06,and 0.08)to stimulate the V^(5+)■V^(2+)reversible multi-electron redox.Such configuration high-entropy can effectively suppress the structural collapse,enhance the redox reversibility in high working voltage(4.0 V),and optimize the electronic induced effect.The in-situ X-ray powder diffraction and in-situ electrochemical impedance spectroscopy tests efficaciously confirm the robust structu ral recovery and far lower polarization throughout an entire charge-discharge cycle during 1.6-4.3 V,respectively.Moreover,the density functional theory calculations clarify the stronger metallicity of high-entropy electrode than the bare that is derived from the more mobile free electrons surrounding the vicinity of Fermi level.By grace of high-entropy design and multi-electron transfer reactions,the optimal Na_(3)V_(1.7)(GaCrAlFeIn)_(0.06)(PO_(4))_(3)can exhibit perfect cycling/rate performances(90.97%@5000 cycles@30 C;112 mA h g^(-1)@10 C and 109 mA h g^(-1)@30 C,2.0-4.3 V).Furthermore,it can supply ultra-high185 mA h g^(-1)capacity with fa ntastic energy density(522 W h kg^(-1))in half-cells(1.4-4.3 V),and competitive capacity(121 mA h g^(-1))as well as energy density(402 W h kg^(-1))in full-cells(1.6-4.1 V),demonstrating enormous application potential for sodium-ion batteries.展开更多
The effects of sulfuric acid concentration, reaction temperature, potential-scanning rate and surfactants on electrochemical behavior of V5+ ion on platinum electrodes were investigated. In voltammetric curves of V5+ ...The effects of sulfuric acid concentration, reaction temperature, potential-scanning rate and surfactants on electrochemical behavior of V5+ ion on platinum electrodes were investigated. In voltammetric curves of V5+ ion there are two reduction peaks corresponding to reductions of V5+ to V4+ （R2） and V5+ to V3+ （R1）, which are irreversible and quasi-reversible processes respectively. Oxidation peak of V3+ to V5+ is intensively affected by pH values on the electrode surface and scanning-potential rates. Only stronger acidity on the electrode surface and faster scanning-potential rates can lead to appearance of this oxidation peak. The neutral surfactant（PCBE） and cationic surfactant（CTAB） retard the V5+ electroreduction. The anionic surfactant（SDS）, even at a very low concentration, increases the currents of both the reduction peaks R1 and R2, and the oxidation peak involves with the oxidation of H2 to H+.展开更多
基金financially supported by the National Key Research and Development Program of China (2022YFA1505700,2019YFA0210403)the National Natural Science Foundation of China (52102216)+1 种基金the Natural Science Foundation of Fujian Province (2022J01625,2022-S-002)the Innovation Training Program for College Students (202310394020,cxxl-2023097,cxxl-2024131,cxxl-2024136)。
文摘Na_(3)V_(2)(PO_(4))_(3)(NVP)is gifted with fast Na^(+)conductive NASICON structure.But it still suffers from low electronic conductivity and inadequate energy density.Herein,a high-entropy modification strategy is realized by doping V^(3+)site with Ga^(3+)/Cr^(3+)/Al^(3+)/Fe^(3+)/In^(3+)simultaneously(i.e.Na_(3)V_(2-x)(GaCrAlFeIn)_x(PO_(4))_(3);x=0,0.04,0.06,and 0.08)to stimulate the V^(5+)■V^(2+)reversible multi-electron redox.Such configuration high-entropy can effectively suppress the structural collapse,enhance the redox reversibility in high working voltage(4.0 V),and optimize the electronic induced effect.The in-situ X-ray powder diffraction and in-situ electrochemical impedance spectroscopy tests efficaciously confirm the robust structu ral recovery and far lower polarization throughout an entire charge-discharge cycle during 1.6-4.3 V,respectively.Moreover,the density functional theory calculations clarify the stronger metallicity of high-entropy electrode than the bare that is derived from the more mobile free electrons surrounding the vicinity of Fermi level.By grace of high-entropy design and multi-electron transfer reactions,the optimal Na_(3)V_(1.7)(GaCrAlFeIn)_(0.06)(PO_(4))_(3)can exhibit perfect cycling/rate performances(90.97%@5000 cycles@30 C;112 mA h g^(-1)@10 C and 109 mA h g^(-1)@30 C,2.0-4.3 V).Furthermore,it can supply ultra-high185 mA h g^(-1)capacity with fa ntastic energy density(522 W h kg^(-1))in half-cells(1.4-4.3 V),and competitive capacity(121 mA h g^(-1))as well as energy density(402 W h kg^(-1))in full-cells(1.6-4.1 V),demonstrating enormous application potential for sodium-ion batteries.
文摘The effects of sulfuric acid concentration, reaction temperature, potential-scanning rate and surfactants on electrochemical behavior of V5+ ion on platinum electrodes were investigated. In voltammetric curves of V5+ ion there are two reduction peaks corresponding to reductions of V5+ to V4+ （R2） and V5+ to V3+ （R1）, which are irreversible and quasi-reversible processes respectively. Oxidation peak of V3+ to V5+ is intensively affected by pH values on the electrode surface and scanning-potential rates. Only stronger acidity on the electrode surface and faster scanning-potential rates can lead to appearance of this oxidation peak. The neutral surfactant（PCBE） and cationic surfactant（CTAB） retard the V5+ electroreduction. The anionic surfactant（SDS）, even at a very low concentration, increases the currents of both the reduction peaks R1 and R2, and the oxidation peak involves with the oxidation of H2 to H+.
