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1.
ACS Appl Mater Interfaces ; 11(45): 42280-42287, 2019 Nov 13.
Artigo em Inglês | MEDLINE | ID: mdl-31682096

RESUMO

Glass and glass-ceramic samples of metastable lithium thiophosphates with compositions of 70Li2S-30P2S5 and Li7P3S11 were controllably prepared by using a rapid assisted-microwave procedure in under 30 min. The rapid preparation times and weak coupling of the evacuated silica ampules with microwave radiation ensure minimal reactivity of the reactants and the container. The microwave-prepared samples display comparable conductivity values with more conventionally prepared (melt quenched) glass and glass-ceramic samples, on the order of 0.1 and 1 mS cm-1 at room temperature, respectively. Rietveld analysis of synchrotron X-ray diffraction data acquired with an internal standard quantitatively yields phase amounts of the glassy and amorphous components, establishing the tunable nature of the microwave preparation. X-ray photoelectron spectroscopy and Raman spectroscopy confirm the composition and the appropriate ratios of isolated and corner-sharing tetrahedra in these semicrystalline systems. Solid-state 7Li nuclear magnetic resonance (NMR) spectroscopy resolves the seven crystallographic Li sites in the crystalline compound into three main environments. The diffusion behavior of these Li environments as obtained from pulsed-field gradient NMR methods can be separated into one slow and one fast component. The rapid and tunable approach to the preparation of high quality "Li7P3S11" samples presented here coupled with detailed structural and compositional analysis opens the door to new and promising metastable solid electrolytes.

2.
ACS Appl Mater Interfaces ; 10(8): 7208-7213, 2018 Feb 28.
Artigo em Inglês | MEDLINE | ID: mdl-29457889

RESUMO

Rapid preparation utilizing assisted microwave heating permits significantly shorter preparation times for magnetocaloric compounds in the (Mn,Fe)2(P,Si) family, specifically samples of (Mn,Fe)2-δP0.5Si0.5 with starting compositions of δ = 0, 0.06, and 0.12. To fully understand the effects of processing and composition changes on structure and properties, these materials are characterized using synchrotron powder diffraction, neutron powder diffraction, electron microprobe analysis (EMPA), X-ray fluorescence (XRF), and magnetic measurements. The diffraction analysis reveals that increasing δ results in decreasing amounts of the common Heusler (Mn,Fe)3Si secondary phase. EMPA shows (Mn,Fe)2(P,Si) in all three samples to be Mn and P rich, whereas XRF demonstrates that the bulk material is Mn rich yet P deficient. Increasing δ brings the Mn/Fe and P/Si ratios closer to their starting values. Measurements of magnetic properties show an increase in saturation magnetization and ordering temperature with increasing δ, consistent with the increase in Fe and Si contents. Increasing δ also results in a decrease in thermal hysteresis and an increase in magnetic entropy change, the latter reaching values close to what have been previously reported on samples that take much longer to prepare.

3.
J Am Chem Soc ; 134(37): 15387-94, 2012 Sep 19.
Artigo em Inglês | MEDLINE | ID: mdl-22909273

RESUMO

Li(2)S is a high-capacity cathode material for lithium metal-free rechargeable batteries. It has a theoretical capacity of 1166 mAh/g, which is nearly 1 order of magnitude higher than traditional metal oxides/phosphates cathodes. However, Li(2)S is usually considered to be electrochemically inactive due to its high electronic resistivity and low lithium-ion diffusivity. In this paper, we discover that a large potential barrier (~1 V) exists at the beginning of charging for Li(2)S. By applying a higher voltage cutoff, this barrier can be overcome and Li(2)S becomes active. Moreover, this barrier does not appear again in the following cycling. Subsequent cycling shows that the material behaves similar to common sulfur cathodes with high energy efficiency. The initial discharge capacity is greater than 800 mAh/g for even 10 µm Li(2)S particles. Moreover, after 10 cycles, the capacity is stabilized around 500-550 mAh/g with a capacity decay rate of only ~0.25% per cycle. The origin of the initial barrier is found to be the phase nucleation of polysulfides, but the amplitude of barrier is mainly due to two factors: (a) charge transfer directly between Li(2)S and electrolyte without polysulfide and (b) lithium-ion diffusion in Li(2)S. These results demonstrate a simple and scalable approach to utilizing Li(2)S as the cathode material for rechargeable lithium-ion batteries with high specific energy.

4.
ACS Nano ; 6(6): 5465-73, 2012 Jun 26.
Artigo em Inglês | MEDLINE | ID: mdl-22558938

RESUMO

Silicon is a promising anode material for Li-ion batteries due to its high theoretical specific capacity. From previous work, silicon nanowires (SiNWs) are known to undergo amorphorization during lithiation, and no crystalline Li-Si product has been observed. In this work, we use an X-ray transparent battery cell to perform in situ synchrotron X-ray diffraction on SiNWs in real time during electrochemical cycling. At deep lithiation voltages the known metastable Li(15)Si(4) phase forms, and we show that avoiding the formation of this phase, by modifying the SiNW growth temperature, improves the cycling performance of SiNW anodes. Our results provide insight on the (de)lithiation mechanism and a correlation between phase evolution and electrochemical performance for SiNW anodes.


Assuntos
Eletrodos , Lítio/química , Nanotecnologia/métodos , Nanotubos/química , Nanotubos/ultraestrutura , Silício/química , Substâncias Macromoleculares/química , Teste de Materiais , Conformação Molecular , Tamanho da Partícula , Propriedades de Superfície , Difração de Raios X
5.
J Am Chem Soc ; 134(14): 6337-43, 2012 Apr 11.
Artigo em Inglês | MEDLINE | ID: mdl-22432568

RESUMO

Rechargeable lithium-sulfur (Li-S) batteries hold great potential for high-performance energy storage systems because they have a high theoretical specific energy, low cost, and are eco-friendly. However, the structural and morphological changes during electrochemical reactions are still not well understood. In this Article, these changes in Li-S batteries are studied in operando by X-ray diffraction and transmission X-ray microscopy. We show recrystallization of sulfur by the end of the charge cycle is dependent on the preparation technique of the sulfur cathode. On the other hand, it was found that crystalline Li(2)S does not form at the end of discharge for all sulfur cathodes studied. Furthermore, during cycling the bulk of soluble polysulfides remains trapped within the cathode matrix. Our results differ from previous ex situ results. This highlights the importance of in operando studies and suggests possible strategies to improve cycle life.

6.
Inorg Chem ; 49(10): 4586-93, 2010 May 17.
Artigo em Inglês | MEDLINE | ID: mdl-20397711

RESUMO

A crystallographic study and theoretical analysis of the Si/Ga site preferences in the Gd(5)Ga(x)Si(4-x) series is presented. Gd(5)Ga(x)Si(4-x) adopt the orthorhombic Gd(5)Si(4)-type structure (space group Pnma, Z = 4) with a maximum Ga content near x = 1.00, as determined by single crystal and powder X-ray diffraction. Refinements from single crystal X-ray diffraction studies of the three independent sites for Si/Ga atoms in the asymmetric unit (interslab T1, intraslab T2 and T3) reveal partial mixing of these elements, with a clear preference for Ga substitution at the interslab T1 sites. To investigate site preferences of Si/Ga atoms, first-principles electronic structure calculations were carried out using the Vienna ab initio simulation package (VASP) and the Stuttgart tight-binding, linear-muffin-tin orbital program with the atomic sphere approximation (TB-LMTO-ASA). Analysis of various crystal orbital Hamilton population (COHP) curves provide some further insights into the structural tendencies and indicate the roles of both sizes and electronegativities of Ga and Si toward influencing the observed upper limit in Ga content in Gd(5)Ga(x)Si(4-x). The magnetic properties of two Gd(5)Ga(x)Si(4-x) phases are also reported: both show ferromagnetic behavior with Curie temperatures lower than that for Gd(5)Si(4).

7.
Acta Crystallogr Sect E Struct Rep Online ; 65(Pt 4): i25, 2009 Mar 06.
Artigo em Inglês | MEDLINE | ID: mdl-21582308

RESUMO

Gd(2)Sc(3)Ge(4) adopts the ortho-rhom-bic Pu(5)Rh(4)-type structure. The crystal structure contains six sites in the asymmetric unit: two sites are statistically occupied by rare-earth atoms with Gd:Sc ratios of 0.967 (4):0.033 (4) and 0.031 (3):0.969 (3), one site (.m. symmetry) is occupied by Sc atoms, and three distinct sites (two of which with .m. symmetry) are occupied by Ge atoms. The rare-earth atoms form two-dimensional slabs with Ge atoms occupying the trigonal-prismatic voids.

8.
J Am Chem Soc ; 130(42): 13900-11, 2008 Oct 22.
Artigo em Inglês | MEDLINE | ID: mdl-18817384

RESUMO

A crystallographic study and theoretical assessment of the Gd/Y site preferences in the Gd 5- x Y x Tt 4 ( Tt = Si, Ge) series prepared by high-temperature methods is presented. All structures for the Gd 5- x Y x Si 4 system belong to the orthorhombic, Gd 5Si 4-type (space group Pnma). For the Gd 5- x Y x Ge 4 system, phases with x < 3.6 and x >or= 4.4 adopt the orthorhombic, Sm 5Ge 4-type structure. For the composition range of 3.6

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