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1.
Acc Chem Res ; 55(5): 696-706, 2022 03 01.
Artigo em Inglês | MEDLINE | ID: mdl-35142507

RESUMO

As one of the most studied materials, research on titanium dioxide (TiO2) has flourished over the years owing to technological interest ranging from energy conversion and storage to medical implants and sensors, to name a few. Within this scope, the development of synthesis routes enabling the stabilization of reactive surface structure has been frequently investigated. Among these routes, solution-based synthesis has been utilized to tailor the material's properties spanning its atomic structural arrangement, or morphological aspects. One of the most investigated methods of stabilizing crystals with tailored facets relies on the use of fluoride-based precursors. Fluoride ions not only provide a driving force for the stabilization of metastable/reactive surface structures but also alter the reactivity of titanium molecular precursors and in turn the structural features of the stabilized crystals. Here, we review recent progress in the solution-based synthesis of anatase (one of the polymorphs of TiO2) employing a fluoride precursor, with an emphasis on how cationic vacancies are stabilized by a charge-compensating mechanism and the resulting structural features associated with these defects. Finally, we will discuss the ion-intercalation properties of these sites with respect to lithium and polyvalent ions such as Mg2+ and Al3+. We will discuss in more detail the relevant parameters of the synthesis that allow controlling the phase composition with the coexistence of oxide, fluoride, and hydroxide ions within the anatase framework. The mechanism of formation of defective anatase nanocrystals has highlighted a solid-state transformation mostly implying an oxolation reaction (the condensation of hydroxide ions) that results in a decrease in the vacancy content, which can be synthetically controlled. The investigation of local fluorine environments probed by solid-state 19F NMR revealed up to three coordination modes with different numbers of coordinated Ti4+ and vacancies. It further revealed the occurrence of single and adjacent pairs of vacancies. These different host sites including native interstitial (and single/paired vacancies) display different ion-intercalation properties. We notably discussed the influence of the local anionic environments of vacancies on the thermodynamics of intercalation properties. The selective intercalation of polyvalent cations such as Mg2+ and Al3+ further supports the beneficial uses of defect chemistry for developing post-lithium-ion batteries. It is expected that the ability to characterize the local structure of defects is key to the design of unique, tailored-made materials.


Assuntos
Fontes de Energia Elétrica , Titânio , Cátions , Lítio , Titânio/química
2.
Chem Mater ; 33(14): 5652-5667, 2021 Jul 27.
Artigo em Inglês | MEDLINE | ID: mdl-34483480

RESUMO

Solid electrolytes are crucial for next-generation solid-state batteries, and Na3PS4 is one of the most promising Na+ conductors for such applications, despite outstanding questions regarding its structural polymorphs. In this contribution, we present a detailed investigation of the evolution in structure and dynamics of Na3PS4 over a wide temperature range 30 < T < 600 °C through combined experimental-computational analysis. Although Bragg diffraction experiments indicate a second-order phase transition from the tetragonal ground state (α, P4̅21 c) to the cubic polymorph (ß, I4̅3m) above ∼250 °C, pair distribution function analysis in real space and Raman spectroscopy indicate remnants of a tetragonal character in the range 250 < T < 500 °C, which we attribute to dynamic local tetragonal distortions. The first-order phase transition to the mesophasic high-temperature polymorph (γ, Fddd) is associated with a sharp volume increase and the onset of liquid-like dynamics for sodium-cations (translational) and thiophosphate-polyanions (rotational) evident by inelastic neutron and Raman spectroscopies, as well as pair-distribution function and molecular dynamics analyses. These results shed light on the rich polymorphism of Na3PS4 and are relevant for a range host of high-performance materials deriving from the Na3PS4 structural archetype.

3.
Inorg Chem ; 60(10): 7217-7227, 2021 May 17.
Artigo em Inglês | MEDLINE | ID: mdl-33956446

RESUMO

The effect of crystallizing solution chemistry on the chemistry of subsequently as-grown materials was investigated for Mo-substituted iron oxides prepared by thermally activated co-precipitation. In the presence of Mo ions, we find that varying the oxidation state of the iron precursor from Fe(II) to Fe(III) causes a progressive loss of atomic long-range order with the stabilization of 2-4 nm particles for the sample prepared with Fe(III). The oxidation state of the Fe precursor also affects the distribution of Fe and Mo cations within the spinel structure. Increasing the Fe precursor oxidation state gives decreased Fe-ion occupation and increased Mo-ion occupation of tetrahedral sites, as revealed by the extended X-ray absorption fine structure. The stabilization of Mo within tetrahedral sites appears to be unexpected, considering the octahedral preferred coordination number of Mo(VI). The analysis of the atomic structure of the sample prepared with Fe(III) indicates a local ordering of vacancies and that the occupation of tetrahedral sites by Mo induces a contraction of the interatomic distances within the polyhedra as compared to Fe atoms. Moreover, the occupancy of Mo into the thermodynamic site preference of a Mo dopant in Fe2O3 assessed by density functional theory calculations points to a stronger preference for Mo substitution at octahedral sites. Hence, we suggest that the synthetized compound is thermodynamically metastable, that is, kinetically trapped. Such a state is suggested to be a consequence of the tetrahedral site occupation by Mo ions. The population of these sites, known to be reactive sites enabling particle growth, is concomitant with the stabilization of very small particles. We confirmed our hypothesis by using a blank experiment without Mo ions, further supporting the impact of tetrahedral Mo ions on the growth of iron oxide nanoparticles. Our findings provide new insights into the relationships between the Fe-chemistry of the crystallizing solution and the structural features of the as-grown Mo-substituted Fe-oxide materials.

4.
Phys Chem Chem Phys ; 23(17): 10498-10508, 2021 May 05.
Artigo em Inglês | MEDLINE | ID: mdl-33899859

RESUMO

Topochemical reactions involving ionic exchange have been used to assess a large number of metastable compositions, particularly in layered metal oxides. This method encompasses complex reactions that are poorly explored, yet are of prime importance to understand and control the materials' properties. In this work, we embark on investigating the reactions involved during the ionic exchange between a layered Na-titanate (lepidocrocite-type structure) and an acidic solution (HCl), leading to a protonic (H3O+) titanate (trititanate structure). The reactions involve an ionic exchange provoking a structural change from the lepidocrocite-type to the trititanate structure as shown by real-space refinements of ex situ pair distribution function data. Mobile Na+ ions are exchanged by hydronium ions inducing high proton mobility in the final structure. Moreover, the reaction was followed by ex situ23Na and 1H solid-state MAS NMR which allowed, among other things, confirming that the Na+ ions are in the interlayer space and specifying their local environment. Strikingly, the ionic exchange reaction induces progressive exfoliation of the Na-titanate particles leading to 2-5 nm thin elongated crystallites. To further understand the different steps associated with the ionic exchange, the evolution of the electrolytic conductivity, using conductimetric titration, has been monitored upon HCl addition, enabling characterization of the intercalation(H+)/de-intercalation(Na+) reactions and assessing kinetic parameters. Accordingly, it is hypothesized that the exfoliation of the particles is due to the accumulation of charges at the particle level in relation to the rapid intercalation of protons. This work provides novel insights into ionic exchange reactions involved in layered oxide compounds.

5.
J Am Chem Soc ; 142(43): 18422-18436, 2020 Oct 28.
Artigo em Inglês | MEDLINE | ID: mdl-33054192

RESUMO

Fast-ion conductors are critical to the development of solid-state batteries. The effects of mechanochemical synthesis that lead to increased ionic conductivity in an archetypical sodium-ion conductor Na3PS4 are not fully understood. We present here a comprehensive analysis based on diffraction (Bragg and pair distribution function), spectroscopy (impedance, Raman, NMR and INS), and ab initio simulations aimed at elucidating the synthesis-property relationships in Na3PS4. We consolidate previously reported interpretations regarding the local structure of ball-milled samples, underlining the sodium disorder and showing that a local tetragonal framework more accurately describes the structure than the originally proposed cubic one. Through variable-pressure impedance spectroscopy measurements, we report for the first time the activation volume for Na+ migration in Na3PS4, which is ∼30% higher for the ball-milled samples. Moreover, we show that the effect of ball-milling on increasing the ionic conductivity of Na3PS4 to ∼10-4 S/cm can be reproduced by applying external pressure on a sample from conventional high-temperature ceramic synthesis. We conclude that the key effects of mechanochemical synthesis on the properties of solid electrolytes can be analyzed and understood in terms of pressure, strain, and activation volume.

6.
Angew Chem Int Ed Engl ; 59(43): 19247-19253, 2020 Oct 19.
Artigo em Inglês | MEDLINE | ID: mdl-32649793

RESUMO

Aluminium batteries constitute a safe and sustainable high-energy-density electrochemical energy-storage solution. Viable Al-ion batteries require suitable electrode materials that can readily intercalate high-charge Al3+ ions. Here, we investigate the Al3+ intercalation chemistry of anatase TiO2 and how chemical modifications influence the accommodation of Al3+ ions. We use fluoride- and hydroxide-doping to generate high concentrations of titanium vacancies. The coexistence of these hetero-anions and titanium vacancies leads to a complex insertion mechanism, attributed to three distinct types of host sites: native interstitial sites, single vacancy sites, and paired vacancy sites. We demonstrate that Al3+ induces a strong local distortion within the modified TiO2 structure, which affects the insertion properties of the neighbouring host sites. Overall, specific structural features induced by the intercalation of highly polarising Al3+ ions should be considered when designing new electrode materials for polyvalent batteries.

7.
RSC Adv ; 10(15): 8982-8988, 2020 Feb 27.
Artigo em Inglês | MEDLINE | ID: mdl-35496548

RESUMO

Chemical doping and other surface modifications have been used to engineer the bulk properties of materials, but their influence on the surface structure and consequently the surface chemistry are often unknown. Previous work has been successful in fluorinating anatase TiO2 with charge balance achieved via the introduction of Ti vacancies rather than the reduction of Ti. Our work here investigates the interface between this fluorinated titanate with cationic vacancies and a monolayer of water via density functional theory based molecular dynamics. We compute the projected density of states for only those atoms at the interface and for those states that fall within 1 eV of the Fermi level for various steps throughout the simulation, and we determine that the variation in this visualization of the density of states serves as a reasonable tool to anticipate where surfaces are most likely to be reactive. In particular, we conclude that water dissociation at the surface is the main mechanism that influences the anatase (001) surface whereas the change in the density of states at the surface of the fluorinated structure is influenced primarily through the adsorption of water molecules.

8.
ACS Omega ; 4(6): 10929-10938, 2019 Jun 30.
Artigo em Inglês | MEDLINE | ID: mdl-31460191

RESUMO

Manipulating the atomic structure of semiconductors is a fine way to tune their properties. The rationalization of their modified properties is, however, particularly challenging as defects locally disrupt the long-range structural ordering, and a deeper effort is required to fully describe their structure. In this work, we investigated the photoelectrochemical properties of an anatase-type structure featuring a high content of titanium vacancies stabilized by dual-oxide substitution by fluoride and hydroxide anions. Such atomic modification induces a slight red-shift band gap energy of 0.08 eV as compared to pure TiO2, which was assigned to changes in titanium-anion ionocovalent bonding. Under illumination, electron paramagnetic resonance spectroscopy revealed the formation of TiIII and O2 - radicals which were not detected in defect-free TiO2. Consequently, the modified anatase shows higher ability to oxidize water with lower electron-hole recombination rate. To further increase the photoelectrochemical properties, we subsequently modified the compound by a surface functionalization with N-methyl-2-pyrrolidone (NMP). This treatment further modifies the chemical composition, which results in a red shift of the band gap energy to 3.03 eV. Moreover, the interaction of the NMP electron-donating molecules with the surface induces an absorption band in the visible region with an estimated band gap energy of 2.25-2.50 eV. Under illumination, the resulting core-shell structure produces a high concentration of reduced TiIII and O2 -, suggesting an effective charge carrier separation which is confirmed by high photoelectrochemical properties. This work provides new opportunities to better understand the structural features that affect the photogenerated charge carriers.

9.
J Phys Chem Lett ; 10(1): 107-112, 2019 Jan 03.
Artigo em Inglês | MEDLINE | ID: mdl-30565946

RESUMO

The properties of crystalline solids can be significantly modified by deliberately introducing point defects. Understanding these effects, however, requires understanding the changes in geometry and electronic structure of the host material. Here we report the effect of forming anion vacancies, via dehydroxylation, in a hexagonal tungsten-bronze-structured iron oxyfluoride, which has potential use as a lithium-ion battery cathode. Our combined pair distribution function and density functional theory analysis indicates that oxygen vacancy formation is accompanied by spontaneous rearrangement of fluorine anions and vacancies, producing dual pyramidal (FeF4)-O-(FeF4) structural units containing 5-fold-coordinated Fe atoms. The addition of lattice oxygen introduces new electronic states above the top of the valence band, with a corresponding reduction in the optical band gap from 4.05 to 2.05 eV. This band gap reduction relative to the FeF3 parent material is correlated with a significant improvement in lithium insertion capability relative to a defect-free compound.

10.
Chem Commun (Camb) ; 54(72): 10080-10083, 2018 Sep 06.
Artigo em Inglês | MEDLINE | ID: mdl-30128472

RESUMO

In anatase TiO2, substituting oxide anions with singly charged (F,OH) anions allows the controlled formation of cation vacancies, which act as reversible intercalation sites for Mg2+. We show that ion-transport (diffusion coefficients) and intercalation (reversible capacity) properties are controlled by two critical parameters: the vacancy concentration and the local anionic environment. Our results emphasise the complexity of this behaviour, and highlight the potential benefits of chemically controlling cationic-defects in electrode materials for rechargeable multivalent-ion batteries.

11.
Nat Mater ; 16(11): 1142-1148, 2017 11.
Artigo em Inglês | MEDLINE | ID: mdl-28920941

RESUMO

In contrast to monovalent lithium or sodium ions, the reversible insertion of multivalent ions such as Mg2+ and Al3+ into electrode materials remains an elusive goal. Here, we demonstrate a new strategy to achieve reversible Mg2+ and Al3+ insertion in anatase TiO2, achieved through aliovalent doping, to introduce a large number of titanium vacancies that act as intercalation sites. We present a broad range of experimental and theoretical characterizations that show a preferential insertion of multivalent ions into titanium vacancies, allowing a much greater capacity to be obtained compared to pure TiO2. This result highlights the possibility to use the chemistry of defects to unlock the electrochemical activity of known materials, providing a new strategy for the chemical design of materials for practical multivalent batteries.

12.
Inorg Chem ; 56(16): 10099-10106, 2017 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-28796492

RESUMO

The potential application of high capacity Sn-based electrode materials for energy storage, particularly in rechargeable batteries, has led to extensive research activities. In this scope, the development of an innovative synthesis route allowing to downsize particles to the nanoscale is of particular interest owing to the ability of such nanomaterial to better accommodate volume changes upon electrochemical reactions. Here, we report on the use of room temperature ionic liquid (i.e., [EMIm+][TFSI-]) as solvent, template, and stabilizer for Sn-based nanoparticles. In such a media, we observed, using Cryo-TEM, that pure Sn nanoparticles can be stabilized. Further washing steps are, however, mandatory to remove residual ionic liquid. It is shown that the washing steps are accompanied by the partial oxidation of the surface, leading to a core-shell structured Sn/SnOx composite. To understand the structural features of such a complex architecture, HRTEM, Mössbauer spectroscopy, and the pair distribution function were employed to reveal a crystallized ß-Sn core and a SnO and SnO2 amorphous shell. The proportion of oxidized phases increases with the final washing step with water, which appeared necessary to remove not only salts but also the final surface impurities made of the cationic moieties of the ionic liquid. This work highlights the strong oxidation reactivity of Sn-based nanoparticles, which needs to be taken into account when evaluating their electrochemical properties.

13.
Inorg Chem ; 55(14): 7182-7, 2016 Jul 18.
Artigo em Inglês | MEDLINE | ID: mdl-27351834

RESUMO

Anatase TiO2 with exposed highly reactive (001) surface is commonly prepared using solution-based synthesis in the presence of a fluorinating agent acting as a structure-directing agent. Recently, the solvothermal reaction of titanium tetraisopropoxide in the presence of aqueous HF has resulted in the stabilization of an oxyhydroxyfluorinated anatase phase featuring cationic vacancies. In the present work, we have studied its formation mechanism, revealing a solid-state transformation of a highly defective anatase phase having a hydroxyfluoride composition that subsequently evolves through an oxolation reaction into an oxyhydroxyfluoride phase. Importantly, this work confirms that titanium alkoxide precursors can react with HF via a fluorolysis process yielding fluorinated molecular precursors, which further condense to produce new composition and structural features deviating from a well-ordered anatase network.

14.
ChemistryOpen ; 4(4): 443-7, 2015 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-26478837

RESUMO

The mechanism of lithium insertion that occurs in an iron oxyfluoride sample with a hexagonal-tungsten-bronze (HTB)-type structure was investigated by the pair distribution function. This study reveals that upon lithiation, the HTB framework collapses to yield disordered rutile and rock salt phases followed by a conversion reaction of the fluoride phase toward lithium fluoride and nanometer-sized metallic iron. The occurrence of anionic vacancies in the pristine framework was shown to strongly impact the electrochemical activity, that is, the reversible capacity scales with the content of anionic vacancies. Similar to FeOF-type electrodes, upon de-lithiation, a disordered rutile phase forms, showing that the anionic chemistry dictates the atomic arrangement of the re-oxidized phase. Finally, it was shown that the nanoscaling and structural rearrangement induced by the conversion reaction allow the in situ formation of new electrode materials with enhanced electrochemical properties.

15.
Inorg Chem ; 54(19): 9619-25, 2015 Oct 05.
Artigo em Inglês | MEDLINE | ID: mdl-26378743

RESUMO

Iron fluoride trihydrate can be used to prepare iron hydroxyfluoride with the hexagonal-tungsten-bronze (HTB) type structure, a potential cathode material for batteries. To understand this phase transformation, a structural description of ß-FeF3·3H2O is first performed by means of DFT calculations and Mössbauer spectroscopy. The structure of this compound consists of infinite chains of [FeF6]n and [FeF2(H2O)4]n. The decomposition of FeF3·3H2O induces a collapse and condensation of these chains, which lead to the stabilization, under specific conditions, of a hydroxyfluoride network FeF3-x(OH)x with the HTB structure. The release of H2O and HF was monitored by thermal analysis and physical characterizations during the decomposition of FeF3·3H2O. An average distribution of FeF4(OH)2 distorted octahedra in HTB-FeF3-x(OH)x was obtained subsequent to the thermal hydrolysis/olation of equatorial anionic positions involving F(-) and H2O. This study provides a clear understanding of the structure and thermal properties of FeF3·3H2O, a material that can potentially bridge the recycling of pickling sludge from the steel industry by preparing battery electrodes.

16.
Sci Rep ; 5: 11553, 2015 Jun 26.
Artigo em Inglês | MEDLINE | ID: mdl-26113411

RESUMO

A highly fluorinated anatase lattice has been recently reported, providing a new class of materials whose general chemical formula is Ti(1-x)□(x)X(4x)O(2-4x) (X(-) = F(-) or OH(-)). To characterise the complex structural features of the material and the different F environments, we here apply a computational screening procedure. After deriving a polarisable force-field from DFT simulations, we screen in a step-wise fashion a large number of possible configurations differing in the positioning of the titanium vacancies (□) and of the fluorine atoms. At each step only 10% of the configurations are retained. At the end of the screening procedure, a configuration is selected and simulated using DFT-based molecular dynamics. This allows us to analyse the atomic structure of the material, which is strongly disordered, leading to a strong decrease (by 0.8 eV) of the band gap compared to conventional anatase.

17.
Dalton Trans ; 43(48): 18025-34, 2014 Dec 28.
Artigo em Inglês | MEDLINE | ID: mdl-25352309

RESUMO

The aim of this work was to investigate the synthesis of tin nanoparticles (NPs) or tin/carbon composites, in room temperature ionic liquids (RTILs), that could be used as structured anode materials for Li-ion batteries. An innovative route for the synthesis of Sn nanoparticles in such media is successfully developed. Compositions, structures, sizes and morphologies of NPs were characterized by high-energy X-ray diffraction (HEXRD), X-ray photoelectron spectroscopy (XPS) and high-resolution transmission electron microscopy (HRTEM). Our findings indicated that (i) metallic tetragonal ß-Sn was obtained and (ii) the particle size could be tailored by tuning the nature of the RTILs, leading to nano-sized spherical particles with a diameter ranging from 3 to 10 nm depending on synthesis conditions. In order to investigate carbon composite materials for Li-ion batteries, Sn nanoparticles were successfully deposited on the surface of multi-wall carbon nanotubes (MWCNT). Moreover, electrochemical properties have been studied in relation to a structural study of the nanocomposites. The poor electrochemical performances as a negative electrode in Li-ion batteries is due to a significant amount of RTIL trapped within the pores of the nanotubes as revealed by XPS investigations. This dramatically affected the gravimetric capacity of the composites and limited the diffusion of lithium. The findings of this work however offer valuable insights into the exciting possibilities for synthesis of novel nano-sized particles and/or alloys (e.g. Sn-Cu, Sn-Co, Sn-Ni, etc.) and the importance of carbon morphology in metal pulverization during the alloying/dealloying process as well as prevention of ionic liquid trapping.

18.
J Am Chem Soc ; 134(10): 4505-8, 2012 Mar 14.
Artigo em Inglês | MEDLINE | ID: mdl-22364225

RESUMO

A new class of selenium and selenium-sulfur (Se(x)S(y))-based cathode materials for room temperature lithium and sodium batteries is reported. The structural mechanisms for Li/Na insertion in these electrodes were investigated using pair distribution function (PDF) analysis. Not only does the Se electrode show promising electrochemical performance with both Li and Na anodes, but the additional potential for mixed Se(x)S(y) systems allows for tunable electrodes, combining the high capacities of S-rich systems with the high electrical conductivity of the d-electron containing Se. Unlike the widely studied Li/S system, both Se and Se(x)S(y) can be cycled to high voltages (up to 4.6 V) without failure. Their high densities and voltage output offer greater volumetric energy densities than S-based batteries, opening possibilities for new energy storage systems that can enable electric vehicles and smart grids.

19.
J Am Chem Soc ; 133(34): 13240-3, 2011 Aug 31.
Artigo em Inglês | MEDLINE | ID: mdl-21809881

RESUMO

The electrochemical reaction of lithium with a vacancy-containing titanium hydroxyfluoride was studied. On the basis of pair distribution function analysis, NMR, and X-ray photoelectron spectroscopy, we propose that the material undergoes partitioning upon initial discharge to form a nanostructured composite containing crystalline Li(x)TiO(2), surrounded by a Ti(0) and LiF layer. The Ti(0) is reoxidized upon reversible charging to an amorphous TiF(3) phase via a conversion reaction. The crystalline Li(x)TiO(2) is involved in an insertion reaction. The resulting composite electrode, Ti(0)-LiF/Li(x)TiO(2) ⇔ TiF(3)/ Li(y)TiO(2), allows reaction of more than one Li per Ti, providing a route to higher capacities while improving the energy efficiency compared to pure conversion chemistries.

20.
Inorg Chem ; 50(13): 5855-7, 2011 Jul 04.
Artigo em Inglês | MEDLINE | ID: mdl-21627151

RESUMO

X-ray pair distribution function (PDF) methods and first-principles calculations have been combined to probe the structure of electrochemically lithiated TiO(2) Brookite. Traditional powder diffraction studies suggest that Brookite amorphizes upon lithium insertion, with the Bragg reflections disappearing. However, PDF analysis indicates that the TiO(2) framework connectivity is maintained throughout lithium intercalation, with expansions along the a and b axes. The Li(+) ions within the framework are poorly observed in the X-ray PDF, which is dominated by contributions from the more strongly scattering Ti and O atoms. First-principles calculations were used to identify energetically favorable Li(+) sites within the Brookite lattice and to develop a complete structural model of the lithiated material. This model replicates the local structure and decreased intermediate range order observed in the PDF data. The analysis suggests that local structural distortions of the TiO(2) lattice accommodate lithium in five-coordinate sites. This structural model is consistent with the observed electrochemical behavior.

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