This paper presents the catalytic effect of NaH doped nanocrystalline TiO_(2)(designated as NaTiOxH)in the improvement of MgH_(2)hydrogen storage properties.The catalyst preparation involves ball milling NaH with TiO_...This paper presents the catalytic effect of NaH doped nanocrystalline TiO_(2)(designated as NaTiOxH)in the improvement of MgH_(2)hydrogen storage properties.The catalyst preparation involves ball milling NaH with TiO_(2)for 3 hr.The addition of 5 wt%NaTiOxH powder into MgH_(2)reduces its operating temperature to∼185℃,which is∼110℃lower than the additive-free as-milled MgH_(2).The composite remarkably desorbs∼7.2 wt%H_(2)within 15 min at∼290℃and reabsorbs∼4.5 wt%H_(2)in 45 min at room temperature under 50 bar H_(2).MgH_(2)dehydrogenation is activated at 57 kJ/mol by the catalyst.More importantly,the addition of 2.5 wt%NaTiOxH catalyst aids MgH_(2)to reversibly produce∼6.1 wt%H_(2)upon 100 cycles within 475 hr at 300℃.Microstructural investigation into the catalyzed MgH_(2)composite reveals a firm contact existing between NaTiOxH and MgH_(2)particles.Meanwhile,the NaTiOxH catalyst consists of catalytically active Ti_(3)O_(5),and“rod-like”Na_(2)Ti_(3)O_(7)species liberated in-situ during preparation;these active species could provide multiple hydrogen diffusion pathways for an improved MgH_(2)sorption process.Furthermore,the elemental characterization identifies the reduced valence states of titanium(Ti<4+)which show some sort of reversibility consistent with H_(2)insertion and removal.This phenomenon is believed to enhance the mobility of Mg/MgH_(2)electrons by the creation and elimination of oxygen vacancies in the defective(TiO_(2-x))catalyst.Our findings have therefore moved MgH_(2)closer to practical applications.展开更多
Fast charging and high volumetric capacity are two of the critical demands for sodium-ion batteries(SIBs).Although nanostructured materials achieve outstanding rate performance,they suffer from low tap density and sma...Fast charging and high volumetric capacity are two of the critical demands for sodium-ion batteries(SIBs).Although nanostructured materials achieve outstanding rate performance,they suffer from low tap density and small volumetric capacity.Therefore,how to realize large volumetric capacity and high tap density simultaneously is very challenging.Here,N/F co-doped TiO_(2)/carbon microspheres(NF- TiO_(2)/C)are synthesized to achieve both of them.Theoretical calculations reveal that N and F co-doping increases the contents of oxygen vacancies and narrows the bandgaps of TiO_(2) and C,improving the electronic conductivity of NF- TiO_(2)/C.Furthermore,NF- TiO_(2)/C exhibits the high binding energy and low diffusion energy barrier of Na+,significantly facilitating Na+storage and Na+diffusion.Therefore,NF- TiO_(2)/C offers a high tap density(1.51 g cm^(-3)),an outstanding rate performance(125.9 mAh g^(-1) at 100 C),a large volumetric capacity(190 mAh cm^(-3) at 100 C),a high areal capacity(4.8 mAh cm^(-2))and an ultra-long cycling performance(80.2%after 10,000 cycles at 10 C)simultaneously.In addition,NF- TiO_(2)/C||Na_(3)V_(2)(PO_(4))_(3) full cells achieve an ultrahigh power density of 25.2 kW kg^(-1).These results indicate the great promise of NF- TiO_(2)/C as a high-volumetric-capacity and high-power-density anode material of SIBs.展开更多
The lanthanum trivalent ion doped TiO2 nanopowders were prepared by liquid plasma spray with solution of titanium tetra-tert-butoxide and alcohol as feedstock and La(NO3)3·6H2O as doping component. The photocatal...The lanthanum trivalent ion doped TiO2 nanopowders were prepared by liquid plasma spray with solution of titanium tetra-tert-butoxide and alcohol as feedstock and La(NO3)3·6H2O as doping component. The photocatalytic activity of samples at different doping concentrations in photocatalytic degradation of methyl orange was discussed. The powders were characterized by Transmission Electron Microscopy (TEM) and X-Ray Diffraction (XRD), and the effect of doped ion on the pattern, phase composition and crystallite sizes were analyzed. The results indicated that lanthanum trivalent ion doped TiO2 nanopowders could be prepared by liquid plasma spray. Lanthanum trivalent ion doping increased the photocatalytic activity of TiO2 greatly, the optimal doping concentration was 0.5%. The doped powders were the mixture of anatase phase and rutile phase. The contents of anatase phase decreased firstly and then increased with an increase in the contents of lanthanum trivalent ion. Doping lanthanum trivalent ion could make the TiO2 nanopowders uniform and reduced its particle size.展开更多
基金The authors acknowledge the Project supported by the National Key R&D Program of China(2019YFE0103600,2018YFB1502101)the Key R&D Program of Shandong Province,China(2020CXGC010402)+4 种基金the National Natural Science Foundation of China(51801197)the Liaoning Revitalization Talents Program(XLYC2002076)the Dalian High-level Talents Program(2019RD09)the Youth Innovation Promotion Association CAS(2019189)K.C.Wong Education Foundation(GJTD-2018–06).
文摘This paper presents the catalytic effect of NaH doped nanocrystalline TiO_(2)(designated as NaTiOxH)in the improvement of MgH_(2)hydrogen storage properties.The catalyst preparation involves ball milling NaH with TiO_(2)for 3 hr.The addition of 5 wt%NaTiOxH powder into MgH_(2)reduces its operating temperature to∼185℃,which is∼110℃lower than the additive-free as-milled MgH_(2).The composite remarkably desorbs∼7.2 wt%H_(2)within 15 min at∼290℃and reabsorbs∼4.5 wt%H_(2)in 45 min at room temperature under 50 bar H_(2).MgH_(2)dehydrogenation is activated at 57 kJ/mol by the catalyst.More importantly,the addition of 2.5 wt%NaTiOxH catalyst aids MgH_(2)to reversibly produce∼6.1 wt%H_(2)upon 100 cycles within 475 hr at 300℃.Microstructural investigation into the catalyzed MgH_(2)composite reveals a firm contact existing between NaTiOxH and MgH_(2)particles.Meanwhile,the NaTiOxH catalyst consists of catalytically active Ti_(3)O_(5),and“rod-like”Na_(2)Ti_(3)O_(7)species liberated in-situ during preparation;these active species could provide multiple hydrogen diffusion pathways for an improved MgH_(2)sorption process.Furthermore,the elemental characterization identifies the reduced valence states of titanium(Ti<4+)which show some sort of reversibility consistent with H_(2)insertion and removal.This phenomenon is believed to enhance the mobility of Mg/MgH_(2)electrons by the creation and elimination of oxygen vacancies in the defective(TiO_(2-x))catalyst.Our findings have therefore moved MgH_(2)closer to practical applications.
基金financial support from the National Nature Science Foundation of China (21971146 and 22105118)the Nature Science Foundation of Shandong Provinces (ZR2021QB095)the China Postdoctoral Science Foundation (2020TQ0183 and 2021M701979)。
文摘Fast charging and high volumetric capacity are two of the critical demands for sodium-ion batteries(SIBs).Although nanostructured materials achieve outstanding rate performance,they suffer from low tap density and small volumetric capacity.Therefore,how to realize large volumetric capacity and high tap density simultaneously is very challenging.Here,N/F co-doped TiO_(2)/carbon microspheres(NF- TiO_(2)/C)are synthesized to achieve both of them.Theoretical calculations reveal that N and F co-doping increases the contents of oxygen vacancies and narrows the bandgaps of TiO_(2) and C,improving the electronic conductivity of NF- TiO_(2)/C.Furthermore,NF- TiO_(2)/C exhibits the high binding energy and low diffusion energy barrier of Na+,significantly facilitating Na+storage and Na+diffusion.Therefore,NF- TiO_(2)/C offers a high tap density(1.51 g cm^(-3)),an outstanding rate performance(125.9 mAh g^(-1) at 100 C),a large volumetric capacity(190 mAh cm^(-3) at 100 C),a high areal capacity(4.8 mAh cm^(-2))and an ultra-long cycling performance(80.2%after 10,000 cycles at 10 C)simultaneously.In addition,NF- TiO_(2)/C||Na_(3)V_(2)(PO_(4))_(3) full cells achieve an ultrahigh power density of 25.2 kW kg^(-1).These results indicate the great promise of NF- TiO_(2)/C as a high-volumetric-capacity and high-power-density anode material of SIBs.
基金the Natural Science Foundation of Shannxi ,China (2005E103)
文摘The lanthanum trivalent ion doped TiO2 nanopowders were prepared by liquid plasma spray with solution of titanium tetra-tert-butoxide and alcohol as feedstock and La(NO3)3·6H2O as doping component. The photocatalytic activity of samples at different doping concentrations in photocatalytic degradation of methyl orange was discussed. The powders were characterized by Transmission Electron Microscopy (TEM) and X-Ray Diffraction (XRD), and the effect of doped ion on the pattern, phase composition and crystallite sizes were analyzed. The results indicated that lanthanum trivalent ion doped TiO2 nanopowders could be prepared by liquid plasma spray. Lanthanum trivalent ion doping increased the photocatalytic activity of TiO2 greatly, the optimal doping concentration was 0.5%. The doped powders were the mixture of anatase phase and rutile phase. The contents of anatase phase decreased firstly and then increased with an increase in the contents of lanthanum trivalent ion. Doping lanthanum trivalent ion could make the TiO2 nanopowders uniform and reduced its particle size.
