Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 23
Filtrar
Mais filtros

Base de dados
Tipo de documento
País de afiliação
Intervalo de ano de publicação
1.
J Am Chem Soc ; 145(13): 7288-7300, 2023 Apr 05.
Artigo em Inglês | MEDLINE | ID: mdl-36876987

RESUMO

Recycling spent lithium-ion batteries (LIBs) has become an urgent task to address the issues of resource shortage and potential environmental pollution. However, direct recycling of the spent LiNi0.5Co0.2Mn0.3O2 (NCM523) cathode is challenging because the strong electrostatic repulsion from a transition metal octahedron in the lithium layer provided by the rock salt/spinel phase that is formed on the surface of the cycled cathode severely disrupts Li+ transport, which restrains lithium replenishment during regeneration, resulting in the regenerated cathode with inferior capacity and cycling performance. Here, we propose the topotactic transformation of the stable rock salt/spinel phase into Ni0.5Co0.2Mn0.3(OH)2 and then back to the NCM523 cathode. As a result, a topotactic relithiation reaction with low migration barriers occurs with facile Li+ transport in a channel (from one octahedral site to another, passing through a tetrahedral intermediate) with weakened electrostatic repulsion, which greatly improves lithium replenishment during regeneration. In addition, the proposed method can be extended to repair spent NCM523 black mass, spent LiNi0.6Co0.2Mn0.2O2, and spent LiCoO2 cathodes, whose electrochemical performance after regeneration is comparable to that of the commercial pristine cathodes. This work demonstrates a fast topotactic relithiation process during regeneration by modifying Li+ transport channels, providing a unique perspective on the regeneration of spent LIB cathodes.

2.
Inorg Chem ; 59(23): 16936-16943, 2020 Dec 07.
Artigo em Inglês | MEDLINE | ID: mdl-33197313

RESUMO

Transition-metal oxalates have wide applications in magnetics, photoemission, electrochemistry, etc. Herein, using hydrothermal reactions, five cobalt(II) oxalates, Na2Co2(C2O4)3·2H2O (I), Na2Co(C2O4)2·8H2O (II), KLi3Co(C2O4)3 (III), Li4Co(C2O4)3 (IV), and (NH4)2Co2(C2O4)F4 (V) have been synthesized, and their structures are determined from single-crystal X-ray diffraction or Rietveld refinement of powder X-ray diffraction data. Notably, IV and V are identified for the first time. The structures of these cobalt oxalates are versatile, covering 0D, 1D, 2D, and 3D frameworks, while the coordination environments of Co2+ centers are uniquely distorted octahedra. As representative examples, I and III are investigated as cathode materials for secondary batteries. Both exhibited electrochemical activity despite large cell polarization. The present study enriches the transition-metal oxalate family and provides new options for energy storage materials.

3.
Angew Chem Int Ed Engl ; 59(24): 9255-9262, 2020 Jun 08.
Artigo em Inglês | MEDLINE | ID: mdl-31976627

RESUMO

Low-cost electrochemical energy storage systems (EESSs) are urgently needed to promote the application of renewable energy sources such as wind and solar energy. In analogy to lithium-ion batteries, the cost of EESSs depends mainly on charge-carrier ions and redox centers in electrodes, and their performance is limited by positive electrodes. In this context, this Minireview evaluates several EESS candidates and summarizes the known mixed polyanionic compounds (MPCs)-a family with robust frameworks and large channels for ion storage and migration. After comprehensive analysis, it is pointed out that a deeper exploration of MPCs may generate numerous novel crystallographically interesting compounds and excellent cathode materials for low-cost energy storage applications.

4.
Angew Chem Int Ed Engl ; 59(2): 740-745, 2020 Jan 07.
Artigo em Inglês | MEDLINE | ID: mdl-31591806

RESUMO

Sodium-ion batteries (NIBs) are the most promising alternatives to lithium-ion batteries in the development of renewable energy sources. The advancement of NIBs depends on the exploration of new electrode materials and fundamental understanding of working mechanisms. Herein, via experimental and simulation methods, we develop a mixed polyanionic compound, Na2 Fe(C2 O4 )SO4 ⋅H2 O, as a cathode for NIBs. Thanks to its rigid three dimensional framework and the combined inductive effects from oxalate and sulfate, it delivered reversible Na insertion/desertion at average discharging voltages of 3.5 and 3.1 V for 500 cycles with Coulombic efficiencies of ca. 99 %. In situ synchrotron X-ray measurements and DFT calculations demonstrate the Fe2+ /Fe3+ redox reactions contribute to electron compensation during Na+ desertion/insertion. The study suggests mixed polyanionic frameworks may provide promising materials for Na ion storage with the merits of low cost and environmental friendliness.

5.
Inorg Chem ; 58(18): 11971-11977, 2019 Sep 16.
Artigo em Inglês | MEDLINE | ID: mdl-31185553

RESUMO

Here we discuss magnetic hybrid coordination frameworks in relation to the realization of new geometrically frustrated magnets. In particular, we present the nuclear and magnetic structures of one such system-the Fe2+-based oxalate fluoride framework KFe(C2O4)F-through analysis of the powder neutron diffraction and muon spectroscopy data. KFe(C2O4)F retains an orthorhombic Cmc21 structure upon cooling to 2 K composed of quasi-one-dimensional iron fluoride chains connected to a distorted triangular network via oxalate anions. Previous magnetometry measurements of KFe(C2O4)F indicate that it is a strongly interacting system with a Weiss constant θ ≈ -300 K that undergoes a magnetic ordering transition at TN ≈ 20 K, yielding a frustration index, f = |θ|/TN ≈ 15, reflective of high-spin frustration. We determine the nature of this frustrated antiferromagnetic ordering below TN and show that the resulting magnetic structure is best described by a model in the Cmc'21' magnetic space group.

6.
Opt Express ; 22(22): 26613-20, 2014 Nov 03.
Artigo em Inglês | MEDLINE | ID: mdl-25401811

RESUMO

We present a numerical simulation of second-harmonic generation (SHG) from a nonlinear magnetic metamaterial. By inserting a second-order nonlinear material in the high local field area of magnetic metamaterial, which consists of periodic arrays of paired thin silver strips, the convertion efficiency of SHG has been significantly enhanced by almost four orders of magnitude. The corresponding field patterns and further studies on dependance between SHG and symmetry of nonlinear crystal show that the increase of the conversion efficiency is attributed to the local field enhancement caused by the magnetic resonnance of the structure. Our researches provide an additional way to further improve the optical nonlinearity in nanostructures.

7.
Inorg Chem ; 53(16): 8197-9, 2014 Aug 18.
Artigo em Inglês | MEDLINE | ID: mdl-25084149

RESUMO

A novel beryllium borate, Ca3Na4LiBe4B10O24F, has been discovered. It possesses a unique ∞(2)[Be8B16O40F2] layer composed of two opposite parallel [Be4B4O12F]∞ layers bridged with [B12O24] polyborates. The linkage of [B12O24] to other structural units is first found in anhydrous borates. In the ∞(2)[Be8B16O40F2] layer, multiple tunnels are arranged along different directions resided by the alkali and alkaline-earth cations. The compound remains stable in an ambient atmosphere from room temperature to the melting point at 830 °C and melts incongruently.

8.
Adv Sci (Weinh) ; 11(1): e2304425, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-37955914

RESUMO

Recycling cathode materials from spent lithium-ion batteries (LIBs) is critical to a sustainable society as it will relief valuable but scarce recourse crises and reduce environment burdens simultaneously. Different from conventional hydrometallurgical and pyrometallurgical recycling methods, direct regeneration relies on non-destructive cathode-to-cathode mode, and therefore, more time and energy-saving along with an increased economic return and reduced CO2 footprint. This review retrospects the history of direct regeneration and discusses state-of-the-art development. The reported methods, including high-temperature solid-state, hydrothermal/ionothermal, molten salt thermochemistry, and electrochemical method, are comparatively introduced, targeting at illustrating their underlying regeneration mechanism and applicability. Further, representative repairing and upcycling studies on wide-applied cathodes, including LiCoO2 (LCO), ternary oxides, LiFePO4 (LFP), and LiMn2 O4 (LMO), are presented, with an emphasis on milestone cases. Despite these achievements, there remain several critical issues that shall be addressed before the commercialization of the mentioned direct regeneration methods.

9.
Adv Mater ; 36(23): e2314247, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38332496

RESUMO

Aqueous dual-ion batteries (ADIBs) based on the cooperative redox of cations and iodine anions at the anode and cathode respectively, are attracting increasing interest because of high capacity and safety. However, the full-cell performance is limited by the sluggish iodine redox kinetics between iodide and polyiodide involving multiple electron transfer steps, and the undesirable shuttling effect of polyiodides. Here, this work reports a versatile conjugated microporous polymer functionalized with secondary amine groups as an organocatalytic cathode for ADIB, which can be positively charged and electrostatically adsorb iodide, and organocatalyze iodine redox reactions through the amine groups. Both theoretical calculations and controlled experiments confirm that the secondary amine groups confine (poly)iodide species via hydrogen bonding, which is essential for accelerating iodine redox kinetics and reducing the polyiodide shuttling effect. The ADIB achieves an ultrahigh capacity of 730 mAh g-1 with an ultrasmall overpotential of 47 mV at 1 A g-1, which also exhibits excellent rate performance and long cycling stability with a capacity retention of 74% after 5000 cycles at a high current density of 5 A g-1. This work demonstrates the promise of developing organocatalysts for accelerating electrochemical processes, which remains a virtually unexplored area in electrocatalyst design for clean energy applications.

10.
J Am Chem Soc ; 135(49): 18319-22, 2013 Dec 11.
Artigo em Inglês | MEDLINE | ID: mdl-24252192

RESUMO

Deep-UV coherent light generated by nonlinear optical (NLO) materials possesses highly important applications in photonic technologies. Beryllium borates comprising anionic planar layers have been shown to be the most promising deep UV NLO materials. Here, two novel NLO beryllium borates Na2Be4B4O11 and LiNa5Be12B12O33 have been developed through cationic structural engineering. The most closely arranged [Be2BO5]∞ planar layers, connected by the flexible [B2O5] groups, have been found in their structures. This structural regulation strategy successfully resulted in the largest second harmonic generation (SHG) effects in the layered beryllium borates, which is ~1.3 and 1.4 times that of KDP for Na2Be4B4O11 and LiNa5Be12B12O33, respectively. The deep-UV optical transmittance spectra based on single crystals indicated their short-wavelength cut-offs are down to ~170 nm. These results demonstrated that Na2Be4B4O11 and LiNa5Be12B12O33 possess very promising application as deep-UV NLO crystals.

11.
Inorg Chem ; 52(15): 8291-3, 2013 Aug 05.
Artigo em Inglês | MEDLINE | ID: mdl-23848160

RESUMO

A new polyborate, Sr8MgB18O36, has been synthesized. Its crystal structure was determined from single-crystal X-ray diffraction data, and characterizations were made by differential scanning calorimetry, Fourier transform IR, UV-vis-near-IR diffuse-reflectance, and first-principles calculations. The structure of Sr8MgB18O36 contains a novel isolated anionic group-an 18-membered ring (B18O36)(18-), which is the first found in borates.

12.
Inorg Chem ; 52(10): 6136-41, 2013 May 20.
Artigo em Inglês | MEDLINE | ID: mdl-23642020

RESUMO

A new polyborate Sr3BeB6O13 has been synthesized and grown by the traditional solid-state reaction method and spontaneous crystallization flux method. It crystallizes in orthorhombic space group Pnma (No. 62) with the following unit cell dimensions: a = 12.775(3) Å, b = 10.029(2) Å, c = 8.0453(16) Å, and Z = 4. The crystal is characterized by an infinite two-dimensional network with a tri-six-membered ring (BeB5O13)(9-) anionic group, which was first found in beryllium borates. Ultraviolet (UV)-visible-near-infrared diffuse reflectance spectroscopy demonstrates that its UV cutoff edge is below 200 nm, and the first-principles electronic structure calculations reveal its energy band gap of 7.03 eV (∼175 nm). Thermal analysis exposes its incongruent feature at 1043 °C. IR spectroscopy measurements are consistent with the crystallographic study. These data reveal that this crystal would be applied as a deep-ultraviolet optical material.

13.
Chem Commun (Camb) ; 58(50): 7074-7077, 2022 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-35662300

RESUMO

We report the first example of a perovskite sulfate [Na3(H2O)]Fe(SO4)3. Further structure modulation, by dimensional reduction or ligand extension, has resulted in two related layered perovskite-like compounds Na6Fe(SO4)4 and Na12Fe3(SO4)6F8. Taken together, these results open up a more general strategy for the future design of more complex perovskite-related materials.

14.
Adv Mater ; 33(2): e2005501, 2021 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-33251702

RESUMO

The urgent demand for cost-effective energy storage devices for large-scale applications has led to the development of several beyond-lithium energy storage systems (EESs). Among them, calcium-ion batteries (CIBs) are attractive due to abundant calcium resources, excellent volumetric and gravimetric capacities of Ca metal anode, and potential high energy density coming from the multivalent feature of Ca-ion. Therefore, the exploration of CIBs electrode materials and the construction of CIBs devices are gaining increasing research interest. Relevant publications cover a wide range of materials by both theoretical and experimental investigations, whereas the performances of rocking-chair CIBs have been unsatisfactory. Meanwhile, multi-ion strategies using more than one ion as the charge carrier have been demonstrated to be feasible and promising options in realizing room temperature CIBs. The summary and reflection of previous studies would provide useful information for future exploration and optimization. In this circumstance, this paper overviews the reported CIBs electrode materials, including both anode and cathode, and presents the latest progress of multi-ion strategies in CIBs. Fundamental challenges, potential solutions, and opportunities are accordingly proposed, mimicking other more mature EESs. This review may promote the development of electrode materials and accelerate the construction of low-cost and high-performance CIBs.

15.
Adv Mater ; 33(24): e2101788, 2021 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-33969548

RESUMO

The intrinsic physical and chemical properties of materials are largely governed by the bonding and electronic structures of their fundamental building units. The majority of cathode materials contain octahedral TMO6 (TM = transition metal), which dominates the redox chemistry during electrochemical operation. As a less symmetric form of TMO6 , the trigonal prismatic geometry is not a traditionally favored coordination configuration as it tends to lose the crystal-field stabilization energy and thus generate large ligand repulsion. Herein, a K-ion battery cathode design, K2 Fe(C2 O4 )2 , is shown​, where the TMO6 trigonal prism (TP) is not only electrochemically active but stable enough to allow for excellent cycling stability. Detailed synchrotron X-ray absorption spectroscopy measurements reveal the evolution of localized fine structure, evidencing the electrochemical activity, reversibility, and stability of the TP motif. The findings are expected to expand the toolbox for the rational design of electrode materials by taking advantage of TP as a structural gene.

16.
Chem Commun (Camb) ; 57(20): 2567-2570, 2021 Mar 09.
Artigo em Inglês | MEDLINE | ID: mdl-33587732

RESUMO

In the title compound, the oxalate ligand simultaneously bridges both Mn-centred and Na-centred octahedra to produce a unique 'doubly-interpenetrated' perovskite-like lattice with an unconventional octahedral tilt system. In turn, the coordination requirements of the oxalate ligand lead to a rare 'twisted' conformation.

17.
Nat Commun ; 11(1): 1225, 2020 Mar 06.
Artigo em Inglês | MEDLINE | ID: mdl-32144250

RESUMO

Potassium-ion batteries are a compelling technology for large scale energy storage due to their low-cost and good rate performance. However, the development of potassium-ion batteries remains in its infancy, mainly hindered by the lack of suitable cathode materials. Here we show that a previously known frustrated magnet, KFeC2O4F, could serve as a stable cathode for potassium ion storage, delivering a discharge capacity of ~112 mAh g-1 at 0.2 A g-1 and 94% capacity retention after 2000 cycles. The unprecedented cycling stability is attributed to the rigid framework and the presence of three channels that allow for minimized volume fluctuation when Fe2+/Fe3+ redox reaction occurs. Further, pairing this KFeC2O4F cathode with a soft carbon anode yields a potassium-ion full cell with an energy density of ~235 Wh kg-1, impressive rate performance and negligible capacity decay within 200 cycles. This work sheds light on the development of low-cost and high-performance K-based energy storage devices.

18.
Nat Commun ; 10(1): 3483, 2019 Aug 02.
Artigo em Inglês | MEDLINE | ID: mdl-31375663

RESUMO

The growing demand for advanced lithium-ion batteries calls for the continued development of high-performance positive electrode materials. Polyoxyanion compounds are receiving considerable interest as alternative cathodes to conventional oxides due to their advantages in cost, safety and environmental friendliness. However, polyanionic cathodes reported so far rely heavily upon transition-metal redox reactions for lithium transfer. Here we show a polyanionic insertion material, Li2Fe(C2O4)2, in which in addition to iron redox activity, the oxalate group itself also shows redox behavior enabling reversible charge/discharge and high capacity without gas evolution. The current study gives oxalate a role as a family of cathode materials and suggests a direction for the identification and design of electrode materials with polyanionic frameworks.

19.
Dalton Trans ; 46(39): 13349-13351, 2017 Oct 10.
Artigo em Inglês | MEDLINE | ID: mdl-28945261

RESUMO

KLi3Fe(C2O4)3 adopts a perovskite-like structure with 1 : 3 ordering of (Li,Fe) on the B-site and (K,vacancy) on the A-site; there are no previous examples of this type of cation ordering in conventional perovskites.

SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA