Das Verhalten der Alkalimetalle zu Kupfer, Silber und Gold

Kienast, Gerhard; Verma, Jitendra Kumar; Klemm, Wilhelm

doi:10.1002/zaac.19613100304

Cited by 191 publications

(84 citation statements)

References 17 publications

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“…8% volume contraction compared to that of pure Au. 38 These data thus suggest that the Li-Au alloy, obtained from the reaction between molten LiBH 4 and Au, is a Au-rich alloy.…”

Section: Resultsmentioning

confidence: 86%

Reactivity of LiBH₄: In Situ Synchrotron Radiation Powder X-ray Diffraction Study

et al. 2008

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Lithium tetrahydridoboranate (LiBH 4 ) may be a potentially interesting material for hydrogen storage, but in order to absorb and desorb hydrogen routinely and reversibly, the kinetics and thermodynamics need to be improved significantly. A priori, this material has one of the highest theoretical gravimetric hydrogen contents, 18.5 wt %, but unfortunately for practical applications, hydrogen release occurs at too high temperature in a non-reversible way. By means of in situ synchrotron radiation powder X-ray diffraction (SR-PXD), the interaction between LiBH 4 and different additivessSiO 2 , TiCl 3 , LiCl, and Ausis investigated. It is found that silicon dioxide reacts with molten LiBH 4 and forms Li 2 SiO 3 or Li 4 SiO 4 at relatively low amounts of SiO 2 , e.g., with 5.0 and 9.9 mol % SiO 2 in LiBH 4 , whereas, for higher amounts of SiO 2 (e.g., 25.5 mol %), only the Li 2 SiO 3 phase is observed. Furthermore, we demonstrate that a solid-state reaction occurs between LiBH 4 and TiCl 3 to form LiCl at room temperature. At elevated temperatures, more LiCl is formed simultaneously with a decrease in the diffracted intensity from TiCl 3 . Lithium chloride shows some solubility in solid LiBH 4 at T > 100°C. This is the first report of substituents that accommodate the structure of LiBH 4 by a solid/solid dissolution reaction. Gold is found to react with molten LiBH 4 forming a Li-Au alloy with CuAu 3 -type structure. These studies demonstrate that molten LiBH 4 has a high reactivity, and finding a catalyst for this H-rich system may be a challenge.

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“…8% volume contraction compared to that of pure Au. 38 These data thus suggest that the Li-Au alloy, obtained from the reaction between molten LiBH 4 and Au, is a Au-rich alloy.…”

Section: Resultsmentioning

confidence: 86%

Reactivity of LiBH₄: In Situ Synchrotron Radiation Powder X-ray Diffraction Study

et al. 2008

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“…stress to the PSCP, as long as the results are independent on the different characteristic times. [21] To interrelate the PSCP and the elastic strain, it is meaningful to multiply Equation 21 with the current density:…”

Section: Discussionmentioning

confidence: 99%

“…Hence the PSCP can be used to calculate an effective η eff as shown in Figure 10. The volume required for creating a substitutional lattice place can be calculated from gold-lithium alloy lattice parameter data 21 to be 99% of the volume of a gold lattice place in the solid solution regime, while the lattice structure is conserved. This corresponds to a η value of 0.33, which is much higher than the highest value in Figure 10 of 0.12.…”

Section: Discussionmentioning

confidence: 99%

The Electro-Chemo-Mechanical Coupling in Lithium Alloy Electrodes and Its Origins

Kitzler

Maawad

Többens

et al. 2015

J. Electrochem. Soc.

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A method to identify and separate the influence of changes in the surface stress from the bulk stress in a model lithium-ion battery electrode during electrochemical cycling was developed. The strategy for this separation is based on the different influence of surface and bulk stresses on the coupling between electrode potential and mechanical strain as measured by dynamic electro-chemo-mechanical analysis and the coupling between the transferred electric charge and the elastic strain as determined by wide angle X-ray scattering. Using both methods, it was possible to uncover the behavior of an apparent surface stress evoked by the bulk stress due to grain boundary alloying of lithium in a gold film. Additionally, the analysis allowed for a determination of a range in surface stress due to underpotential deposition of one monolayer of lithium as the interval between −3.1 to Lithium-ion batteries are widely used, though the amount of electric charge they can store is still far away from their theoretical capacity.1,2 In order to increase the capacity of lithium-ion battery anodes, the commonly used graphite needs to be replaced. A very promising alternative are materials which can form alloys with lithium. 3,4 There are several possible candidates. 5 Among the most important ones are silicon, germanium, tin, aluminum, and antimony. The theoretical volumetric lithium storage capacity of these materials is several times higher than that of the currently used anodes. In case of silicon, more than ten times that of graphite relative to the weight of the host material. This storage capability of the afore mentioned materials is based on their ability to store more than one, in case of silicon, germanium, and tin up to 4.4 lithium atoms per host atom. The obvious drawback of these materials is the huge volume change during lithium loading which can easily exceed 100%.If the electrode material is constrained (e.g. by the current collector) or the lithium is inhomogeneously distributed in the host material, the change in volume is accompanied by stresses.6 Possible consequences are the evolution of cracks in the material which can lead to pulverization of the electrode material and consequently loss of capacity. 6 A promising possibility to prevent pulverization is to reduce the structure size of the electrode material and to introduce high porosity. 7,8 High porosity reduces concentration gradients by reducing the diffusion lengths and it weakens the constraints by offering free space in the vicinity of the electrode. However, this strategy also increases the surface to volume ratio, and therefore drastically increases the impact of the surface stress, which can have an important impact on the stability of the electrode material.9 Additionally, the stress interacts with the chemical potential via the strain energy. 10 Therefore, the equilibrium lithium concentration is a function of the stress state which, in general, is inhomogeneous within the electrode material. Recent simulations performed by Gau and Zhou 11 indicat...

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“…Im System R ubidium -G old [2,3] sind bisher n u r die V erbindungen R b A u [4] und R b A u 5 [5,6] ein deutig nachgewiesen und strukturell c h a ra k te ri siert w orden. Die Existenz von R b A u 2 [2,3,7] ko n n te bisher nicht verifiziert werden.…”

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“…Die Existenz von R b A u 2 [2,3,7] ko n n te bisher nicht verifiziert werden. D ie h o m o logen V erbindungen N aA u 2 [8] und K A u 2 [9] sind Lavesphasen und kristallisieren im kubischen M gC u2-Typ bzw.…”

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Gold-Alkalimetallsysteme, III. Hochdrucksynthese und Kristallstruktur von Rb₃Au₇ [1] / Gold-Alkali Metal-Systems, III. High Pressure Synthesis and Crystal Structure of Rb₃Au₇ [1]

Range

Grosch

Rau

et al. 1994

Zeitschrift Für Naturforschung B

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The intermetallic compound Rb3Au7 could be synthesized from the elements at 4 kbar, 700 °C in a modified Belt-type apparatus. The structure (Cmmm; a = 5.579(1), b = 13.267(5), c = 7.265(2) Å; Z = 2; R = 0.035, Rw = 0,031) comprises three crystallographically independent Au atoms, arranged in layers along the c-axis. The shortest interatomic distances are Au -Au = 2.633Å, Au -Rb = 3.438Å and Rb -Rb = 3.622Å.

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Das Verhalten der Alkalimetalle zu Kupfer, Silber und Gold

Cited by 191 publications

References 17 publications

Reactivity of LiBH₄: In Situ Synchrotron Radiation Powder X-ray Diffraction Study

Reactivity of LiBH₄: In Situ Synchrotron Radiation Powder X-ray Diffraction Study

The Electro-Chemo-Mechanical Coupling in Lithium Alloy Electrodes and Its Origins

Gold-Alkalimetallsysteme, III. Hochdrucksynthese und Kristallstruktur von Rb₃Au₇ [1] / Gold-Alkali Metal-Systems, III. High Pressure Synthesis and Crystal Structure of Rb₃Au₇ [1]

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Das Verhalten der Alkalimetalle zu Kupfer, Silber und Gold

Cited by 191 publications

References 17 publications

Reactivity of LiBH4: In Situ Synchrotron Radiation Powder X-ray Diffraction Study

Reactivity of LiBH4: In Situ Synchrotron Radiation Powder X-ray Diffraction Study

The Electro-Chemo-Mechanical Coupling in Lithium Alloy Electrodes and Its Origins

Gold-Alkalimetallsysteme, III. Hochdrucksynthese und Kristallstruktur von Rb3Au7 [1] / Gold-Alkali Metal-Systems, III. High Pressure Synthesis and Crystal Structure of Rb3Au7 [1]

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Reactivity of LiBH₄: In Situ Synchrotron Radiation Powder X-ray Diffraction Study

Reactivity of LiBH₄: In Situ Synchrotron Radiation Powder X-ray Diffraction Study

Gold-Alkalimetallsysteme, III. Hochdrucksynthese und Kristallstruktur von Rb₃Au₇ [1] / Gold-Alkali Metal-Systems, III. High Pressure Synthesis and Crystal Structure of Rb₃Au₇ [1]