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  • 1
    Online Resource
    Online Resource
    Walter de Gruyter GmbH ; 2012
    In:  Zeitschrift für Physikalische Chemie Vol. 226, No. 5-6 ( 2012-6-1), p. 461-489
    In: Zeitschrift für Physikalische Chemie, Walter de Gruyter GmbH, Vol. 226, No. 5-6 ( 2012-6-1), p. 461-489
    Abstract: Single crystals of titanium disulfide TiS 2 were synthesized by chemical vapor synthesis and subsequently intercalated with n-butyl lithium (BuLi) in n-hexane. Experiments were carried out using a butyl lithium concentration between 0.8 and 10 mol L -1 and the temperature range was from 248 K to 328 K. The duration of the intercalation was varied from 2 h to 30 d. After the intercalation experiments concentration profiles of lithium, titanium and sulfur were measured parallel to the ab-plane of the crystal by LA-ICP-OES (LASER Ablation — Inductively Coupled Plasma - Optical Emission Spectroscopy). Chemical diffusion coefficients ( D ) were determined by fitting of the profiles to the specific solution of Fick's 2 nd law for the given boundary conditions. The measured diffusivity in the ab-plane ( D || a/b ) varies between 10 -13 and 10 -15 m 2 s -1 at room temperature. These variations of D cannot be correlated to the reaction time. On the other hand a systematic increase of D || a/b with the concentration of butyl lithium ( c BuLi ) was observed, with a corresponding decrease in activation energy from 59.6 ± 7.6 kJ mol -1 ( c BuLi =1.6 mol L -1 ) to 42.6 ± 11.7 kJ mol -1 ( c BuLi =10 mol L -1 ). Furthermore, profiles measured on the same crystals reveal D || a/b values differing by up to a factor of 3. ToF-SIMS (Time-of-Flight Secondary Ion Mass Spectromety) images gave evidence of inhomogenous insertion of lithium along crystal edges. These findings indicate that stress induced by widening of the crystal layers plays a crucial role in the intercalation kinetics. SIMS profiling perpendicular to the ab-plane gives evidence that D ⊥ a /b is at least four orders of magnitude lower than D || a/b .
    Type of Medium: Online Resource
    ISSN: 2196-7156 , 0942-9352
    RVK:
    Language: English
    Publisher: Walter de Gruyter GmbH
    Publication Date: 2012
    detail.hit.zdb_id: 201103-7
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  • 2
    Online Resource
    Online Resource
    American Chemical Society (ACS) ; 2013
    In:  The Journal of Physical Chemistry B Vol. 117, No. 48 ( 2013-12-05), p. 15184-15195
    In: The Journal of Physical Chemistry B, American Chemical Society (ACS), Vol. 117, No. 48 ( 2013-12-05), p. 15184-15195
    Type of Medium: Online Resource
    ISSN: 1520-6106 , 1520-5207
    RVK:
    Language: English
    Publisher: American Chemical Society (ACS)
    Publication Date: 2013
    detail.hit.zdb_id: 1357799-2
    detail.hit.zdb_id: 2006039-7
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  • 3
    Online Resource
    Online Resource
    Walter de Gruyter GmbH ; 2017
    In:  Zeitschrift für Physikalische Chemie Vol. 231, No. 7-8 ( 2017-7-26), p. 1303-1321
    In: Zeitschrift für Physikalische Chemie, Walter de Gruyter GmbH, Vol. 231, No. 7-8 ( 2017-7-26), p. 1303-1321
    Abstract: In order to improve our understanding of the Li-mobility in oxide glass networks with Li as the principle mobile particle, electrical conductivity and self-diffusivity of lithium was studied in two phosphate (0.2 Li 2 O·0.8 P 2 O 5 , 0.3 Li 2 O·0.2 MgO·0.5 P 2 O 5 ) and one borate (0.25 Li 2 O·0.75 B 2 O 3 ) glass compositions. Conductivity measurements provided information about ion dynamics while isotope-exchange experiments involving isotopically enriched Li diffusion glass couples provided information about long-range diffusivity of Li-isotopes through borate and phosphate networks. Due to the limitations of individual glass stabilities, the temperature range for selected experiments was very small, e.g. as in the case of Li–phosphate composition between 373 and 520 K. The activation energy for Li-migration derived from conductivity measurements was similar for Li–Mg–phosphate and Li–borate, 90.4 and 85.2 kJ/mol, while for pure Li–phosphate the value was 74.7 kJ/mol. In the case of self-diffusion, the activation energies were comparable with Li–Mg–phosphate having the highest value of 76.9 kJ/mol while Li–phosphate and Li–borate had almost the same value of 72.9 and 72.2 kJ/mol, respectively. In these glass compositions with similar Li-cation concentration, the differences in the mobility predominantly depend on structural arrangement of building units and the spatial distribution of negative potentials, as reflected in the value of H R / f , i.e. the Haven ratio divided by the correlation factor, as a mean to better understand the diffusion mechanism in glass structures, where vacancy vs. interstitial diffusion cannot be clearly defined. For Li–phosphate almost unconstrained Li-migration was indicated with the H R / f value of 0.98, while Li–Mg–phosphate had the most structural constraint on mobilized Li-cations, with the H R / f value of 0.30. Findings are compared with silicate (Li 2 O·3 SiO 2 ) and aluminosilicate (Li 2 O·Al 2 O 3· 4 SiO 2 ) glasses from our previous studies in order to elaborate the effect of network topology.
    Type of Medium: Online Resource
    ISSN: 2196-7156 , 0942-9352
    RVK:
    Language: English
    Publisher: Walter de Gruyter GmbH
    Publication Date: 2017
    detail.hit.zdb_id: 201103-7
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  • 4
    Online Resource
    Online Resource
    Walter de Gruyter GmbH ; 2017
    In:  Zeitschrift für Physikalische Chemie Vol. 231, No. 7-8 ( 2017-7-26), p. 1345-1359
    In: Zeitschrift für Physikalische Chemie, Walter de Gruyter GmbH, Vol. 231, No. 7-8 ( 2017-7-26), p. 1345-1359
    Abstract: Reaction with n-butyl lithium (BuLi) is commonly used to study the kinetics of intercalation of lithium in electrode materials for batteries. We performed lithium isotope exchange experiments on TiS 2 single crystals as model system to determine the irreversible step in the intercalation process. Single crystals of TiS 2 were prepared by chemical vapor transport and intercalated by lithium with natural isotopic signature (7% 6 Li 93% 7 Li) using a 2.5 molar solution of BuLi in hexane. Crystals were homogenized at 313 K in a dry argon atmosphere for 1–2 months and then exposed for several days to ~1 molar BuLi solution enriched in the light lithium isotope (95% 6 Li, 5% 7 Li). After the isotopic exchange experiments concentration profiles of the isotopes were measured parallel to the a/b-plane of the crystal using Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS). Profiles show that already intercalated lithium isotopes can be completely exchanged without significant increase in total lithium content. This observation implies that, after adsorption of BuLi at the crystal surface, the butyl radical can freely jump from one lithium atom to a neighbouring one. The jump sequence is either finished by desorption of a BuLi molecule or by combination of two adjacent butyl radicals forming an octane molecule or other kinds of deactivation of butyl radicals. The latter step is irreversible. Self diffusion coefficients determined by fitting of the lithium isotope profiles are in good agreement with chemical diffusivities determined by lithium intercalation experiments.
    Type of Medium: Online Resource
    ISSN: 2196-7156 , 0942-9352
    RVK:
    Language: English
    Publisher: Walter de Gruyter GmbH
    Publication Date: 2017
    detail.hit.zdb_id: 201103-7
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  • 5
    In: Earth and Planetary Science Letters, Elsevier BV, Vol. 561 ( 2021-05), p. 116846-
    Type of Medium: Online Resource
    ISSN: 0012-821X
    RVK:
    Language: English
    Publisher: Elsevier BV
    Publication Date: 2021
    detail.hit.zdb_id: 300203-2
    detail.hit.zdb_id: 1466659-5
    SSG: 16,13
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  • 6
    Online Resource
    Online Resource
    Walter de Gruyter GmbH ; 2015
    In:  Zeitschrift für Physikalische Chemie Vol. 229, No. 9 ( 2015-9-28), p. 1289-1312
    In: Zeitschrift für Physikalische Chemie, Walter de Gruyter GmbH, Vol. 229, No. 9 ( 2015-9-28), p. 1289-1312
    Abstract: Chemical intercalation of lithium in single crystals of TiX 2 (X = S, Se, Te) was studied at pressures of 10–500 MPa and temperatures of 293–363 K. Crystals were synthesized by chemical vapor synthesis and cut with a LASER into squares (2.2 × 2.2 mm). Samples and 1.6 mol · L – 1 n-butyl lithium solutions in n-hexane (BuLi) were sealed in gold capsules. Experiments were carried out in cold seal pressure vessels for 5–20 days using Ar as pressure medium. A large fraction of samples showed degradation after the experiments, i.e., at low pressures and at high temperatures. On samples with minor degradation, lithium profiles were measured parallel to the crystallographic ab-plane , using femtosecond-LASER Ablation-Inductively Coupled Plasma-Optical Emission Spectroscopy and -Mass Spectrometry (fs-LA-ICP-OES and -MS). Most of the profiles could be well fitted by the specific solution of Fick's second law for the given boundary conditions. Lithium diffusivities ( D Li ) and lithium contents at the crystal edges ( x Li,S ) were determined from the fits. At 500 MPa and room temperature lithium diffusivities are similar in TiS 2 ((1.07 to 2.41) × 10 – 15  m 2  · s – 1 ) and TiSe 2 ((1.48 to 2.10) × 10 – 15  m 2  · s – 1 ) but significantly lower in TiTe 2 ((0.07 to 0.55) × 10 – 15  m 2  · s – 1 ). Moreover, diffusivity of Li in TiTe 2 decreases significantly with increasing pressure whereas for the other chalcogenides a pressure dependence cannot be evidenced. Lithium surface contents are lower for TiS 2 ( x   =  0.15 to 0.36) than for TiSe 2 (0.66 to 0.71) and TiTe 2 (0.59 to 0.99), slightly elevated compared to ambient pressure experiments. These findings indicate, that the ionicity of the Ti–X bonding as well as the size of the interlayer space (van der Waals gap) play a crucial role for the degree of lithium insertion and for the pressure dependence of lithium diffusivity.
    Type of Medium: Online Resource
    ISSN: 0942-9352 , 2196-7156
    RVK:
    Language: English
    Publisher: Walter de Gruyter GmbH
    Publication Date: 2015
    detail.hit.zdb_id: 201103-7
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  • 7
    In: European Journal of Mineralogy, Schweizerbart, Vol. 17, No. 2 ( 2005-04-29), p. 233-242
    Type of Medium: Online Resource
    ISSN: 0935-1221
    Uniform Title: Trace element diffusion in rhyolitic melts: comparison between synchrotron radiation X-ray fluorescence microanalysis (-SRXRF) and secondary ion mass spectrometry (SIMS)
    RVK:
    Language: English , English
    Publisher: Schweizerbart
    Publication Date: 2005
    detail.hit.zdb_id: 1000286-8
    detail.hit.zdb_id: 2039451-2
    SSG: 13
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  • 8
    In: American Mineralogist, Mineralogical Society of America, Vol. 105, No. 8 ( 2020-08-1), p. 1126-1139
    Abstract: Transport and deposition of copper in the Earth's crust are mainly controlled by the solubility of Cu-bearing phases and the speciation of Cu in magmatic-hydrothermal fluids. To improve our understanding of copper mobilization by hydrothermal fluids, we conducted an experimental study on the interaction between Cu-bearing phases (metallic copper, Cu2O, CuCl) and aqueous chloride solutions (H2O ± NaCl ± HCl; with Cl concentrations of 0 to 4.3 mol kg-1). The experiments were run in rapid heat/rapid quench cold-seal pressure vessels at 800 °C, 200 MPa, and logfO2 ~ NNO+2.3. Either Cu or Au capsules were used as containers. The reaction products were sampled in situ by the entrapment of synthetic fluid inclusions in quartz. Fluid composition was subsequently determined by analyzing individual fluid inclusions using a freezing cell and laser ablation inductively coupled plasma-mass spectrometry. Our results show that large isolated and isometric inclusions, free of late-stage modifications, can be preserved after the experiment even when using a high cooling rate of 25 K s-1. The obtained results demonstrate that: (1) reaction between native Cu, NaCl solution, and quartz (± silica gel) leads to the coexistence of fluid inclusions and Na-bearing silicate melt inclusions. Micrometer-to submicrometer-sized cuprite (Cu2O) crystals have been observed in both types of the inclusions, and they are formed most probably due to the dissociation of CuOH. (2) When Cu0 reacts with HCl and CuCl solutions, or Cu+ reacts with NaCl solution, nantokite (CuCl) formed due to oversaturation has been found in fluid inclusion. Copper concentration in the fluid shows a strong positive dependence on the initial chlorine content, with Cu/Cl molal ratios varying from 1:9 to 1:1 in case 1 and case 2, respectively. When Cl is fixed to 1.5 m, initial fluid acidity has a major control on the Cu content, i.e., 0.17 ± 0.09 and 1.29 ± 0.57 m Cu were measured in fluids of case 1 and case 2, respectively. Cu solubility in pure water and in 1.5 m NaCl solutions are 0.004 ± 0.002 and 0.16 ± 0.07 m, respectively. The main responsible Cu-bearing complexes are CuOH(H2O)x in water, NaCuCl2 in NaCl solutions and HCuCl2 in alkali-free solutions. These results provide quantitative constraints on the mobility of Cu in hydrothermal solutions and confirm that Cl is a very important ligand responsible for Cu transport. The first observation that silicate melt can be generated in the fluid-dominated and native-copper-bearing system implies that transitional thermosilicate liquids can coexist with metal-rich fluids and may enhance Cu mobility in magmatic-hydrothermal systems. This may have important implications for the formation of Cu deposits in the systems with low S activities.
    Type of Medium: Online Resource
    ISSN: 0003-004X , 1945-3027
    RVK:
    Language: English
    Publisher: Mineralogical Society of America
    Publication Date: 2020
    detail.hit.zdb_id: 3514-2
    detail.hit.zdb_id: 2045960-9
    SSG: 13
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  • 9
    Online Resource
    Online Resource
    Elsevier BV ; 2020
    In:  Earth and Planetary Science Letters Vol. 538 ( 2020-05), p. 116213-
    In: Earth and Planetary Science Letters, Elsevier BV, Vol. 538 ( 2020-05), p. 116213-
    Type of Medium: Online Resource
    ISSN: 0012-821X
    RVK:
    Language: English
    Publisher: Elsevier BV
    Publication Date: 2020
    detail.hit.zdb_id: 300203-2
    detail.hit.zdb_id: 1466659-5
    SSG: 16,13
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