The most stable isomers of NanBm （m ＋ n = 6） clusters and their hydrogen storage properties are investigated by means of density functional theory with a 6-311＋G（d） basis set. To study the hydrogen storage prope...The most stable isomers of NanBm （m ＋ n = 6） clusters and their hydrogen storage properties are investigated by means of density functional theory with a 6-311＋G（d） basis set. To study the hydrogen storage properties, all of the stable structures of NanBmHx （m ＋ n =6） clusters have been optimized. It shows that boron atoms of NanBm are separated from the other boron atoms, and form satellite BHx （x = 3, 4） clusters around the centre, which attach to the system by a bridging bond of a hydrogen atom or an Na atom. Compared with the hydrogen storage capabilities, the Na3B3 has the highest hydrogen storage capacity among NanBm clusters. The binding energies, interaction energies of hydrogen atom with NanBm clusters and second difference in energy of Na3B3Hx clusters have been calculated. The results show that the stability of the NanBmHx clusters present an odd-even oscillatory effect, as the number of H atoms increases.展开更多
Na_(3)V_(2)(PO_(4))_(3)(NVP),as a great potential cathode candidate for Na-ion batteries(NIBs),has attracted enormous interest due to its three-dimensional(3D)large open framework for convenient Na+transport,yet its p...Na_(3)V_(2)(PO_(4))_(3)(NVP),as a great potential cathode candidate for Na-ion batteries(NIBs),has attracted enormous interest due to its three-dimensional(3D)large open framework for convenient Na+transport,yet its practical application is still limited by its inferior electron conductivity and sluggish Na+diffusion kinetics.Herein,the tiny Cr doped hierarchical NVP micro-flower cathodes(i.e.,Na_(3)V_(2-x)Crx(PO_(4))_(3)@C,x≤0.1),which are self-assembled with single-crystal nanoflake subunits in-situ coated with carbon nano-shell,are designed and fabricated via a scalable avenue.The optimized cathode,i.e.,Na_(3)V_(1.94)Cr_(0.06)(PO_(4))_(3)@C(NVCP-6),was endowed with more electro-active Na(2)sites and higher electronic/ionic conductivity for efficient sodium storage.Benefiting from these competitive merits,the NVCP-6,when evaluated as a cathode towards NIBs,exhibits an ultrahigh-rate capability of 99.8 mAh·g^(-1)at 200 C and superior stability of 82.2%over 7300 cycles at 50 C.Furthermore,the NVCP-6 based full NIBs display remarkable electrochemical properties in terms of both high-rate capacities and long-duration cycling properties at different temperatures(-20–50°C).The contribution,i.e.,the design of“four ounces can move a thousand pounds”,here will promote the practical industrial application of NVP towards advanced NIBs.展开更多
基金supported by the National Natural Science Foundation of China (Grant Nos. 10965002 and 30960031)the Science Foundation of Education Committee of Jiangxi Province,China (Grant No. GJJ10540)the Doctoral Startup Fund of Jinggangshan University
文摘The most stable isomers of NanBm （m ＋ n = 6） clusters and their hydrogen storage properties are investigated by means of density functional theory with a 6-311＋G（d） basis set. To study the hydrogen storage properties, all of the stable structures of NanBmHx （m ＋ n =6） clusters have been optimized. It shows that boron atoms of NanBm are separated from the other boron atoms, and form satellite BHx （x = 3, 4） clusters around the centre, which attach to the system by a bridging bond of a hydrogen atom or an Na atom. Compared with the hydrogen storage capabilities, the Na3B3 has the highest hydrogen storage capacity among NanBm clusters. The binding energies, interaction energies of hydrogen atom with NanBm clusters and second difference in energy of Na3B3Hx clusters have been calculated. The results show that the stability of the NanBmHx clusters present an odd-even oscillatory effect, as the number of H atoms increases.
基金supported by the National Natural Science Foundation of China(Nos.51904115,52072151,52171211,52271218,and U22A20145)Taishan Scholars(No.ts201712050)+1 种基金Jinan Independent Innovative Team(No.2020GXRC015)Major Program of Shandong Province Natural Science Foundation(No.ZR2021ZD05).
文摘Na_(3)V_(2)(PO_(4))_(3)(NVP),as a great potential cathode candidate for Na-ion batteries(NIBs),has attracted enormous interest due to its three-dimensional(3D)large open framework for convenient Na+transport,yet its practical application is still limited by its inferior electron conductivity and sluggish Na+diffusion kinetics.Herein,the tiny Cr doped hierarchical NVP micro-flower cathodes(i.e.,Na_(3)V_(2-x)Crx(PO_(4))_(3)@C,x≤0.1),which are self-assembled with single-crystal nanoflake subunits in-situ coated with carbon nano-shell,are designed and fabricated via a scalable avenue.The optimized cathode,i.e.,Na_(3)V_(1.94)Cr_(0.06)(PO_(4))_(3)@C(NVCP-6),was endowed with more electro-active Na(2)sites and higher electronic/ionic conductivity for efficient sodium storage.Benefiting from these competitive merits,the NVCP-6,when evaluated as a cathode towards NIBs,exhibits an ultrahigh-rate capability of 99.8 mAh·g^(-1)at 200 C and superior stability of 82.2%over 7300 cycles at 50 C.Furthermore,the NVCP-6 based full NIBs display remarkable electrochemical properties in terms of both high-rate capacities and long-duration cycling properties at different temperatures(-20–50°C).The contribution,i.e.,the design of“four ounces can move a thousand pounds”,here will promote the practical industrial application of NVP towards advanced NIBs.
