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1.
Adv Sci (Weinh) ; : e2206096, 2023 Jan 03.
Artigo em Inglês | MEDLINE | ID: mdl-36594619

RESUMO

The construction of strong interactions and synergistic effects between small metal clusters and supports offers a great opportunity to achieve high-performance and cost-effective heterogeneous catalysis, however, studies on its applications in electrocatalysis are still insufficient. Herein, it is reported that W18 O49 nanowires supported sub-nanometric Ru clusters (denoted as Ru SNC/W18 O49 NWs) constitute an efficient bifunctional electrocatalyst for hydrogen evolution/oxidation reactions (HER and HOR) under acidic condition. Microstructural analyses, X-ray absorption spectroscopy, and density functional theory (DFT) calculations reveal that the Ru SNCs with an average RuRu coordination number of 4.9 are anchored to the W18 O49 NWs via RuOW bonds at the interface. The strong metal-support interaction leads to the electron-deficient state of Ru SNCs, which enables a modulated RuH strength. Furthermore, the unique proton transport capability of the W18 O49 also provides a potential migration channel for the reaction intermediates. These components collectively enable the remarkable performance of Ru SNC/W18 O49 NWs for hydrogen electrocatalysis with 2.5 times of exchange current density than that of carbon-supported Ru nanoparticles, and even rival the state-of-the-art Pt catalyst. This work provides a new prospect for the development of supported sub-nanometric metal clusters for efficient electrocatalysis.

2.
Inorg Chem ; 61(50): 20538-20546, 2022 Dec 19.
Artigo em Inglês | MEDLINE | ID: mdl-36480275

RESUMO

The crystal structure and superconducting properties of a new type of titanium-pnictide superconductor, BaTi2(Sb1-yBiy)2O (y = 0.2, 0.5, and 0.8), are comprehensively investigated over a wide pressure range to elucidate the effect of substituting Bi for Sb on the superconducting behavior. The behavior of superconducting properties under pressure changes drastically with y, as expected from the double-dome Tc-y phase diagram obtained at ambient pressure. In this study, three BaTi2(Sb1-yBiy)2O samples (y = 0.2, 0.5, and 0.8) are considered, which correspond to the first superconducting dome, nonsuperconducting part, and second superconducting dome, respectively, in the Tc-y phase diagram. The crystal of BaTi2(Sb1-yBiy)2O with y = 0.2 shows a clear collapse transition, i.e., a drastic shrinkage of the lattice constant c at ca. 5 GPa. Strictly speaking, the collapsed crystal phase coexists with the noncollapsed phase above 5 GPa. On the other hand, BaTi2(Sb1-yBiy)2O with y = 0.8 shows a continuous change in the crystal lattice with pressure, i.e., no collapse transitions. The pressure dependence of Tc for BaTi2(Sb1-yBiy)2O with y = 0.2 shows a drastic increase in Tc at approximately 5 GPa, where the collapse transition occurs, indicating a clear pressure-induced superconducting phase transition related to the collapse transition. The value of Tc for BaTi2(Sb1-yBiy)2O with y = 0.8 increases slightly up to ∼2 GPa and is almost constant at 2-13 GPa. It is found that the superconducting behavior under pressure can be unambiguously classified by y based on the double-dome Tc-y phase diagram, indicative of distinguishable superconducting features at different y values. In this study, we comprehensively discuss the superconducting properties of the exotic material, BaTi2(Sb1-yBiy)2O, with a double-dome Tc-y phase diagram.

3.
Phys Chem Chem Phys ; 24(12): 7185-7194, 2022 Mar 23.
Artigo em Inglês | MEDLINE | ID: mdl-35262150

RESUMO

The structural and superconducting properties of alkali-Bi-based compounds, KBi2 and RbBi2, were investigated over a wide pressure range for the first time. The samples of KBi2 and RbBi2 were prepared using a liquid ammonia (NH3) technique, and demonstrated superconductivity with superconducting transition temperatures, Tc, of 3.50 and 4.21 K at ambient pressure, respectively. The onset superconducting transition temperature, Tconset, of KBi2 decreased slightly; however, it suddenly jumped at 2 GPa and increased gradually with pressure, indicating the presence of two superconducting phases in the low-pressure range. The pressure-dependent X-ray diffraction patterns indicate that the KBi2 sample decomposed into KBi and Bi at pressures higher than 2.5 GPa. Moreover, a discontinuous change in Tconset was observed for KBi2 at 9 GPa, which reflects the decomposition of KBi2 into KBi and Bi. By contrast, the value of Tconset of RbBi2 was almost constant over a pressure range of 0-8 GPa. Thus, the superconducting properties and stability of alkali-Bi-based compounds against pressure were comprehensively explored in this study. In addition, the superconducting Cooper pair symmetry was investigated from the magnetic field dependence of Tc of KBi2 at 0.790 and 2.32 GPa, and of RbBi2 at 1.17 GPa, indicating the exact deviation from the simple s-wave paring model, which may be due to the complex electronic structure of Bi. The results elucidated the exotic superconducting properties of KBi2 and RbBi2 based on the pressure and magnetic field dependence of Tc and verified the chemical stability of KBi2 under pressure.

4.
Adv Sci (Weinh) ; 9(6): e2104522, 2022 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-35018738

RESUMO

Engineering of structure and composition is essential but still challenging for electrocatalytic activity modulation. Herein, hybrid nanostructured arrays (HNA) with branched and aligned structures constructed by cobalt selenide (CoSe2 ) nanotube arrays vertically oriented on carbon cloth with CoNi layered double hydroxide (CoSe2 @CoNi LDH HNA) are synthesized by a hydrothermal-selenization-hybridization strategy. The branched and hollow structure, as well as the heterointerface between CoSe2 and CoNi LDH guarantee structural stability and sufficient exposure of the surface active sites. More importantly, the strong interaction at the interface can effectively modulate the electronic structure of hybrids through the charge transfer and then improves the reaction kinetics. The resulting branched CoSe2 @CoNi LDH HNA as trifunctional catalyst exhibits enhanced electrocatalytic performance toward oxygen evolution/reduction and hydrogen evolution reaction. Consequently, the branched CoSe2 @CoNi LDH HNA exhibits low overpotential of 1.58 V at 10 mA cm-2 for water splitting and superior cycling stability (70 h) for rechargeable flexible Zn-air battery. Theoretical calculations reveal that the construction of heterostructure can effectively lower the reaction barrier as well as improve electrical conductivity, consequently favoring the enhanced electrochemical performance. This work concerning engineering heterostructure and topography-performance relationship can provide new guidance for the development of multifunctional electrocatalysts.

5.
J Am Chem Soc ; 144(5): 2255-2263, 2022 Feb 09.
Artigo em Inglês | MEDLINE | ID: mdl-35094512

RESUMO

Noble metals have an irreplaceable role in catalyzing electrochemical reactions. However, large overpotential and poor long-term stability still prohibit their usage in many reactions (e.g., oxygen evolution/reduction). With regard to the low natural abundance, the improvement of their overall electrocatalytic performance (activity, selectivity, and stability) was urgently necessary. Herein, strong metal-support interaction (SMSI) was modulated through an unprecedented time-dependent mechanical milling method on Pd-loaded oxygenated TiC electrocatalysts. The encapsulation of Pd surfaces with reduced TiO2-x overlayers is precisely controlled by the mechanical milling time. This encapsulation induced a valence band restructuring and lowered the d-band center of surface Pd atoms. For hydrogen peroxide electrosynthesis through the two-electron oxygen reduction reaction (ORR), these electronic and geometric modifications resulted in optimal adsorption energies of reaction intermediates. Thus, SMSI phenomena not only enhanced electrocatalytic activity and selectivity but also created an encapsulating oxide overlayer that protected the Pd species, increasing its long-term stability. This SMSI induced by mechanical milling was also extended to other noble metal systems, showing great promise for the large-scale production of highly stable and tunable electrocatalysts.

6.
ACS Appl Mater Interfaces ; 13(19): 23173-23180, 2021 May 19.
Artigo em Inglês | MEDLINE | ID: mdl-33955729

RESUMO

This work demonstrated the enhanced photodegradation (PD) resulting from Co-rich doping of ZnO nanowire (NW) surfaces (Co2+/ZnO NWs) prepared by combining Co sputtering on ZnO NWs and immersion in deionized water to exploit the hydrophilic-hydrophobic transitions on the ZnO surfaces resulting from Co atom diffusion. Because of the controllable spin-dependent density of states (DOS) induced by Co2+, the PD of methylene blue dye can be enhanced by approximately 90% (when compared with bare ZnO NWs) by using a conventional permanent magnet with a relatively low magnetic field strength of approximately 0.15 T. The reliability of spin polarization-modulation attained through surface doping, based on the magnetic response observed from X-ray absorption measurements and magnetic circular dichroism, provides an opportunity to create highly efficient catalysts by engineering surfaces and tailoring their spin-dependent DOS.

7.
Small ; 17(10): e2007239, 2021 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-33590684

RESUMO

Since the sluggish kinetic process of oxygen reduction (ORR)/evolution (OER) reactions, the design of highly-efficient, robust, and cost-effective catalysts for flexible metal-air batteries is desired but challenging. Herein, bimetallic nanoparticles encapsulated in the N-doped hollow carbon nanocubes (e.g., FeCo-NPs/NC, FeNi-NPs/NC, and CoNi-NPs/NC) are rationally designed via a general heat-treatment strategy of introducing NH3 pyrolysis of dopamine-coated metal-organic frameworks. Impressively, the resultant FeCo-NPs/NC hybrid exhibits superior bifunctional electrocatalytic performance for ORR/OER, manifesting exceptional discharging performance, outstanding lifespan, and prime flexibility for both Zn/Al-air batteries, superior to those of state-of-the-art Pt/C and RuO2 catalysts. X-ray absorption near edge structure and density functional theory indicate that the strong synergy between FeCo alloy and N-doped carbon frameworks has a distinctive activation effect on bimetallic Fe/Co atoms to synchronously modify the electronic structure and afford abundant dual-active Fe/Co-Nx sites, large surface area, high nitrogen doping level, and conductive carbon frameworks to boost the reversible oxygen electrocatalysis. Such N-doped carbon with bimetallic alloy bonds provides new pathways for the rational creation of high-efficiency energy conversion and storage equipment.

8.
Inorg Chem ; 60(6): 3585-3592, 2021 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-33615782

RESUMO

We investigated the pressure dependence of electric transport in a superconducting sample, Ba0.77Na0.23Ti2Sb2O, to complete the phase diagram of superconducting transition temperature (Tc) against pressure (p). This superconducting sample exhibits a Tc value of 5.8 K at ambient pressure. Here, the superconductivity of the recently reported sample was investigated over a wide pressure range. The Tc value monotonously decreased with pressure below 8 GPa. Interestingly, the Tc value rapidly increased above 8 GPa and slowly declined with pressure above 11 GPa. Thus, a new superconducting phase was discovered above ∼9 GPa. The crystal structure of Ba0.77Na0.23Ti2Sb2O was also elucidated at 0-22.0 GPa with synchrotron X-ray powder diffraction. Consequently, an evident relation between the crystal structure and the superconductivity was revealed, namely, a clear structural phase transition was observed at 8-11 GPa, where the Tc value rapidly increased against pressure. This study provides detailed information on the superconductivity of Ba0.77Na0.23Ti2Sb2O under pressure, which will lead to a comprehensive understanding of pressure-driven superconductivity.

9.
ACS Appl Mater Interfaces ; 13(6): 7355-7369, 2021 Feb 17.
Artigo em Inglês | MEDLINE | ID: mdl-33534550

RESUMO

Ni-rich high-energy-density lithium ion batteries pose great risks to safety due to internal short circuits and overcharging; they also have poor performance because of cation mixing and disordering problems. For Ni-rich layered cathodes, these factors cause gas evolution, the formation of side products, and life cycle decay. In this study, a new cathode electrolyte interphase (CEI) for Ni2+ self-oxidation is developed. By using a branched oligomer electrode additive, the new CEI is formed and prevents the reduction of Ni3+ to Ni2+ on the surface of Ni-rich layered cathode; this maintains the layered structure and the cation mixing during cycling. In addition, this new CEI ensures the stability of Ni4+ that is formed at 100% state of charge in the crystal lattice at high temperature (660 K); this prevents the rock-salt formation and the over-reduction of Ni4+ to Ni2+. These findings are obtained using in situ X-ray absorption spectroscopy, operando X-ray diffraction, operando gas chromatography-mass spectroscopy, and X-ray photoelectron spectroscopy. Transmission electron microscopy reveals that the new CEI has an elliptical shape on the material surface, which is approximately 100 nm in length and 50 nm in width, and covers selected particle surfaces. After the new CEI was formed on the surface, the Ni2+ self-oxidation gradually affects from the surface to the bulk of the material. It found that the bond energy and bond length of the Ni-O are stabilized, which dramatically inhibit gas evolution. The new CEI is successfully applied in a Ni-rich layered compound, and the 18650- and the punch-type full cells are fabricated. The energy density of the designed cells is up to 300 Wh/kg. Internal short circuit and overcharging safety tests are passed when using the standard regulations of commercial evaluation. This new CEI technology is ready and planned for future applications in electric vehicle and energy storage.

10.
Artigo em Inglês | MEDLINE | ID: mdl-33412533

RESUMO

The topological insulator PdBi2exhibits two different crystal phases at ambient pressure, i.e., "α-PdBi2" and "ß-PdBi2." The pressure dependence of crystal structure and superconductivity of α-PdBi2has been fully elucidated thus far. However, the physical properties of ß-PdBi2crystals under pressure have not been sufficiently investigated. In this study, we fully investigate the crystal structure and superconductivity of ß-PdBi2under pressure based on synchrotron X-ray diffraction (XRD) patterns. The temperature dependence of ß-PdBi2indicates its superconductivity with a superconducting transition temperature (Tc) as high as 4.10 K, and its crystal structure is tetragonal (space group ofI4/mmm (No. 139)). The XRD patterns at 0 - 22.0 GPa indicate no structural phase transitions, and the unit cell volume shrinks monotonically with pressure, unlike the behavior of α-PdBi2. Furthermore, α-PdBi2transformed to ß-PdBi2under pressure. This suggests that ß-PdBi2is stable under pressure. The superconductivity is clearly observed at 0 - 11.8 GPa, and the value ofTcis almost constant at ~4.4 K. The temperature dependence of the upper critical field at ambient pressure and 10.7 GPa indicate that the superconductivity is not attributed to a simples-wave dirty limit but ans-wave clean orp-wave polar model. This is the first systematic study of superconductivity of topological insulator ß-PdBi2under pressure.

11.
J Phys Condens Matter ; 33(13): 135702, 2021 Jan 29.
Artigo em Inglês | MEDLINE | ID: mdl-33511965

RESUMO

The topological insulator PdBi2 exhibits two different crystal phases at ambient pressure, i.e., 'α-PdBi2' and ' -PdBi2'. The pressure dependence of crystal structure and superconductivity of α-PdBi2 has been fully elucidated thus far. However, the physical properties of ß-PdBi2 crystals under pressure have not been sufficiently investigated. In this study, we fully investigate the crystal structure and superconductivity of ß-PdBi2 under pressure based on synchrotron x-ray diffraction (XRD) patterns. The temperature dependence of ß-PdBi2 indicates its superconductivity with a superconducting transition temperature (T c) as high as 4.10 K, and its crystal structure is tetragonal [space group of I4/mmm (no. 139)]. The XRD patterns at 0-22.0 GPa indicate no structural phase transitions, and the unit cell volume shrinks monotonically with pressure, unlike the behavior of α-PdBi2. Furthermore, α-PdBi2 transformed to ß-PdBi2 under pressure. This suggests that ß-PdBi2 is stable under pressure. The superconductivity is clearly observed at 0-11.8 GPa, and the value of T c is almost constant at ∼4.4 K. The temperature dependence of the upper critical field at ambient pressure and 10.7 GPa indicates that the superconductivity is not attributed to a simple s-wave dirty limit but an s-wave clean or p-wave polar model. This is the first systematic study of superconductivity of topological insulator ß-PdBi2 under pressure.

12.
Sci Rep ; 11(1): 1929, 2021 Jan 21.
Artigo em Inglês | MEDLINE | ID: mdl-33479432

RESUMO

The abnormal lattice expansion of commercial polypropylene (PP)/polyethylene (PE)/polypropylene (PP) separator in lithium-ion battery under different charging current densities was observed by in-situ X-ray diffraction. Significant lattice changes of both PP and PE were found during the low current density charging. The capacity fading and the resistance value of the cell measured at 0.025 C (5th retention, 92%) is unexpectedly larger than that at 1.0 C (5th retention, 97.3%) from the electrochemical impedance spectroscopic data. High-resolution scanning electron microscopy is employed to witness the pore changes of the trilayered membrane. Density functional theory calculations were used to investigate the mechanism responsible for the irregular results. The calculations revealed that the insertion of Li-ion and EC molecule into PP or PE are thermodynamically favourable process which might explain the anomalous significant lattice expansion during the low current density charging. Therefore, designing a new separator material with a more compact crystalline structure or surface modification to reduce the Li insertion during the battery operation is desirable.

13.
J Phys Condens Matter ; 33(48)2021 Sep 22.
Artigo em Inglês | MEDLINE | ID: mdl-34492649

RESUMO

The crystal structures of Sb2Te3-ySey(y= 0.6 andy= 1.2) at 0-24 GPa were investigated by synchrotron x-ray diffraction. The stoichiometry of Sb2Te3-ySeyused in this study was determined to be Sb2Te2.19(9)Se0.7(2)fory= 0.6 and Sb2Te1.7(1)Se1.3(3)fory= 1.2, on the basis of energy-dispersive x-ray spectroscopy. The sample of Sb2Te2.19(9)Se0.7(2)showed a structural phase transition from a rhombohedral structure (space group No. 166,R3¯m) (phase I) to a monoclinic structure (space group No. 12,C2/m) (phase II), with increasing pressure up to ∼9 GPa. A new structural phase (phase II') emerged at 17.7 GPa, a monoclinic structure with the space groupC2/c(No. 15). Finally, a 9/10-fold monoclinic structure (space group No. 12,C2/m) (phase III) was observed at 21.8 GPa. In contrast, the sample of Sb2Te1.7(1)Se1.3(3)provided only phase I (space group No. 166,R3¯m) and phase II (space group No. 12,C2/m), showing one structural phase transition from 0-19.5 GPa. These samples were not superconductors at ambient pressure, but superconductivity suddenly appeared with increasing pressure. Superconductivity with superconducting transition temperatures (Tc's) of 2 and 4 K was observed above 6 GPa in phase I of Sb2Te2.19(9)Se0.7(2). In this sample, theTcvalues of 6 and 9 K were observed in phase II and phase II' or III of Sb2Te2.19(9)Se0.7(2), respectively. Superconductivity withTc's of 4 and 5 K suddenly emerged in Sb2Te1.7(1)Se1.3(3)at 13.6 GPa, which corresponds to phase II, and it evolved to 6.0 K under further increased pressure. ATcvalue of 9 K was finally found above 15 GPa. The magnetic field dependence ofTcin phase II of Sb2Te2.19(9)Se0.7(2)and Sb2Te1.7(1)Se1.3(3)followed ap-wave polar model, suggesting topologically nontrivial superconductivity.

14.
ACS Nano ; 15(9): 14996-15006, 2021 Sep 28.
Artigo em Inglês | MEDLINE | ID: mdl-34515484

RESUMO

The active phase and catalytic mechanisms of Ni-based layered double hydroxide (LDH) materials for oxygen evolution reaction (OER) have no common consensus and remain controversial. Moreover, engineering the site activity and the number of active sites of LDHs is an efficient approach to advance the OER activity, as the thickness and stacking structure of the LDHs layer limit the catalytic activity. This work presents an interesting in situ approach of tuning the site activity and number of active sites of NiMn-LDHs, which exhibit the superior OER performance (onset overpotential of 0.17 V and overpotential of 0.24 V at 10 mA cm-2). The fundamental mechanistic insights and active phases during the OER process are characterized by in operando techniques along with the computational density functional theory calculations, revealing that the Ni site constitutes the OER activity and the dynamically generated NiOOH moiety is the active phase. We also prove that Ni sites undergo a reversible oxidation state under the working conditions to create active NiOOH species which catalyze the water to generate oxygen. These findings suggest that the Ni(III) phase in NiMn-LDHs is the OER active site and Mn promotes the electronic properties of Ni sites. Utilizing in situ/in operando techniques and theoretical calculation, we find that the in situ intercalation of guest anions allows the expansion of the LDH layers and keeps the active NiOOH species under the oxidation state of +3 via electron coupling, which ultimately tunes the site populations and site activity toward the superior OER activity, respectively. This work thus targets to provide insight into strategies to design the next generation of highly active catalysts for water electrolysis and fuel cell technologies.

15.
Phys Chem Chem Phys ; 23(40): 23014-23023, 2021 Oct 20.
Artigo em Inglês | MEDLINE | ID: mdl-34612269

RESUMO

Herein, we report the preparation and characterization of BaBi3 clarified by DC magnetic susceptibility, powder X-ray diffraction (XRD), and electrical transport. The superconducting properties of BaBi3 were elucidated through the magnetic and electrical transport properties in a wide pressure range. The superconducting transition temperature, Tc, showed a slight decrease (or almost constant Tc) against pressure up to 17.2 GPa. The values of the upper critical field, Hc2, at 0 K, were determined to be 1.27 T at 0 GPa and 3.11 T at 2.30 GPa, using the formula, because p-wave pairing appeared to occur for this material at both pressures, indicating the unconventionality of superconductivity. This result appears to be consistent with the topological non-trivial nature of superconductivity predicted theoretically. The pressure-dependent XRD patterns measured at 0-20.1 GPa indicated no structural phase transitions up to 20.1 GPa, i.e., the structural phase transitions from the α phase to the ß or γ phase which are induced by an application of pressure were not observed, contrary to the previous report, demonstrating that the α phase is maintained over the entire pressure range. Admittedly, the lattice constants and the volume of the unit cell, V, steadily decrease with increasing pressure up to 20.1 GPa. In this study, the plots of Tcversus p and V versus p of BaBi3 are depicted over a wide pressure range for the first time.

16.
Glob Chall ; 4(10): 2000025, 2020 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-33033627

RESUMO

The rarely explored, spin-polarized band engineering, enables direct dynamic control of the magneto-optical absorption (MOA) and associated magneto-photocurrent (MPC) by a magnetic field, greatly enhancing the range of applicability of photosensitive semiconductor materials. It is demonstrated that large negative and positive MOA and MPC effects can be tuned alternately in amorphous carbon ( a-C )/ZnO nanowires by controlling the sp2/sp3 ratio of a-C . A sizeable enhancement of the MPC ratio (≈15%) appears at a relatively low magnetic field (≈0.2 T). Simulated two peaks spin-polarized density of states is applied to explain that the alternate sign switching of the MOA is mainly related to the charge transfer between ZnO and C. The results indicate that the enhanced magnetic field performance of ( a-C )/ZnO nanowires may have applications in renewable energy-related fields and tunable magneto-photonics.

17.
Phys Chem Chem Phys ; 22(40): 23315-23322, 2020 Oct 21.
Artigo em Inglês | MEDLINE | ID: mdl-33034332

RESUMO

A new superconducting sample, BaTi2Bi2O, was synthesized and characterized over a wide pressure range. The superconducting transition temperature, Tc, of BaTi2Bi2O was 4.33 K at ambient pressure. The crystal structure was tetragonal (space group of P4/mmm (No. 123)), according to the X-ray diffraction (XRD) pattern at ambient pressure. The XRD pattern was analyzed using the Le Bail method. The magnetic-field dependence of the magnetization at different temperatures was precisely investigated to elucidate the characteristics of the superconductivity. The pressure-dependent XRD patterns showed absence of structural phase transitions up to 19.8 GPa. The superconducting properties of BaTi2Bi2O were investigated under pressure. Tc monotonously increased with the pressure (p) up to 4.0 GPa and saturated above 4.0 GPa. The variations in the Tc-p plot were thoroughly analyzed. The Cooper pair symmetry (or superconducting pairing mechanism) was analyzed based on the magnetic field dependence of the superconductivity at ambient and high pressures, which indicated a sign of p-wave pairing for the superconductivity of BaTi2Bi2O, i.e., topologically nontrivial sign was suggested for BaTi2Bi2O.

18.
ACS Appl Mater Interfaces ; 12(36): 40296-40309, 2020 Sep 09.
Artigo em Inglês | MEDLINE | ID: mdl-32841558

RESUMO

Polyoxometalates (POMs) have emerged as potential anode materials for lithium-ion batteries (LIBs) owing to their ability to transfer multiple electrons. Although POM anode materials exhibit notable results in LIBs, their energy-storage mechanisms have not been well-investigated. Here, we utilize various in operando and ex situ techniques to verify the charge-storage mechanisms of a Keplerate-type POM Na2K23{[(MoVI)MoVI5O21(H2O)3(KSO4)]12 [(VIVO)30(H2O)20(SO4)0.5]}·ca200H2O ({Mo72V30}) anode in LIBs. The {Mo72V30} anode provides a high reversible capacity of up to ∼1300 mA h g-1 without capacity fading for up to 100 cycles. The lithium-ion storage mechanism was studied systematically through in operando synchrotron X-ray absorption near-edge structure, ex situ X-ray diffraction, ex situ extended X-ray absorption fine structure, ex situ transmission electron microscopy, in operando synchrotron transmission X-ray microscopy, and in operando Raman spectroscopy. Based on the abovementioned results, we propose that the open hollow-ball structure of the {Mo72V30} molecular cluster serves as an electron/ion sponge that can store a large number of lithium ions and electrons reversibly via multiple and reversible redox reactions (Mo6+ ↔ Mo1+ and V5+/V4+↔ V1+) with fast lithium diffusion kinetics (DLi+: 10-9-10-10 cm2 s-1). No obvious volumetric expansion of the microsized {Mo72V30} particle is observed during the lithiation/delithiation process, which leads to high cycling stability. This study provides comprehensive analytical methods for understanding the lithium-ion storage mechanism of such complicated POMs, which is important for further studies of POM electrodes in energy-storage applications.

19.
J Phys Condens Matter ; 32(46): 465702, 2020 Jul 30.
Artigo em Inglês | MEDLINE | ID: mdl-32731210

RESUMO

The crystal structure of BiSbTeSe2 (Bi2-x Sb x Te3-y Se y (x = 1.0 and y = 2.0)) at 0-29 GPa is investigated through synchrotron x-ray diffraction (XRD) and two structural phase transitions are discovered. The stoichiometry of BiSbTeSe2 employed in this study is Bi1.19(4)Sb0.81(4)Te0.83(4)Se2.17(4), as determined from energy-dispersive x-ray spectroscopy. The sample demonstrated structural transitions, from a rhombohedral structure (space group no 166, R [Formula: see text] m) (phase I) to a monoclinic structure (space group no 12, C2/m) (phase II), and from phase II to a 9/10-fold monoclinic structure (space group no 12, C2/m) (phase III). The temperature dependence of resistance (R-T plot) exhibited a semiconducting behavior in a low pressure range and changed from semiconducting to metallic behavior with increasing pressure. Pressure-driven superconductivity is observed above 9.1 GPa in Bi1.19(4)Sb0.81(4)Te0.83(4)Se2.17(4). The pressure phase corresponds to phase II. The superconducting transition temperature, T c, increased with pressure. The maximum T c value is 8.3 K at 19.1 GPa. The magnetic field dependence of T c in phase II of Bi1.19(4)Sb0.81(4)Te0.83(4)Se2.17(4) is proceeded by a p-wave polar model, indicating topologically nontrivial superconductivity. In addition, the emergence of superconductivity and the change in superconducting behavior are closely associated with the structural transitions.

20.
J Phys Condens Matter ; 32(39): 395704, 2020 Jun 03.
Artigo em Inglês | MEDLINE | ID: mdl-32492659

RESUMO

We synthesized the alkaline-earth metal-doped FeSe compounds (NH3) y AE x FeSe (AE: Ca, Sr and Ba), using the liquid NH3 technique, to determine their superconducting properties and crystal structures. Multiple superconducting phases were obtained in each sample of (NH3) y Ca x FeSe and (NH3) y Ba x FeSe, which showed two superconducting transition temperatures (T c's) as high as 37-39 K and 47-48 K at ambient pressure, hereinafter referred to as the 'low-T c phase' and 'high-T c phase', respectively. The high-T c phases in (NH3) y Ca x FeSe and (NH3) y Ba x FeSe were metastable, and rapidly converted to their low-T c phases. However, T c values of 38.4 K and 35.6 K were recorded for (NH3) y Sr x FeSe, which displayed different behavior than (NH3) y Ca x FeSe and (NH3) y Ba x FeSe. The Le Bail fitting of x-ray diffraction (XRD) patterns provided lattice constants of c = 16.899(1) Å and c = 16.8630(8) Å for the low-T c phases of (NH3) y Ca x FeSe and (NH3) y Ba x FeSe, respectively. The lattice constants of their high-T c phases could not be determined due to the disappearance of the high T c phase within a few days. The XRD pattern for (NH3) y Sr x FeSe indicated the coexistence of two phases with c = 16.899(3) Å and c = 15.895(4) Å. The former value of c in (NH3) y Sr x FeSe is almost the same as those of the low-T c phases in (NH3) y Ca x FeSe and (NH3) y Ba x FeSe. Therefore, the phase with c = 16.899(3) Å in (NH3) y Sr x FeSe must correspond to the superconducting phase with the T c of 38.4 K, while the superconducting phase with T c = 35.6 K is assigned to the crystal phase with c = 15.895(4) Å. For (NH3) y Sr x FeSe, a high-T c phase with T c = 47-48 K has not yet been obtained, but a new phase showing the T c value of 35.6 K was clearly obtained. This is the first systematic study of the preparation, crystal structure, and superconductivity of alkaline-earth metal-doped FeSe, (NH3) y AE x FeSe.

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