Details
| Originalsprache | Englisch |
|---|---|
| Seiten (von - bis) | 461-489 |
| Seitenumfang | 29 |
| Fachzeitschrift | Zeitschrift fur Physikalische Chemie |
| Jahrgang | 226 |
| Ausgabenummer | 5-6 |
| Publikationsstatus | Veröffentlicht - 1 Juni 2012 |
Abstract
Single crystals of titanium disulfide TiS2 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 10mol 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 2nd 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 (cBuLi) was observed, with a corresponding decrease in activation energy from 59.6±7.6 kJmol-1 (cBuLi = 1.6molL-1) to 42.6±11.7 kJmol-1 (cBuLi = 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 Spectrometry) 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 Da/b is at least four orders of magnitude lower than D||a/b.
ASJC Scopus Sachgebiete
- Chemie (insg.)
- Physikalische und Theoretische Chemie
Zitieren
- Standard
- Harvard
- Apa
- Vancouver
- BibTex
- RIS
in: Zeitschrift fur Physikalische Chemie, Jahrgang 226, Nr. 5-6, 01.06.2012, S. 461-489.
Publikation: Beitrag in Fachzeitschrift › Artikel › Forschung › Peer-Review
}
TY - JOUR
T1 - Kinetics of Lithium Intercalation in Titanium Disulfide Single Crystals
AU - Schwarzburger, Nele Isabell
AU - Knobel, Robert
AU - Behrens, Harald
AU - Binnewies, Michael
AU - Horn, Ingo
AU - Pelster, Andreas
AU - Arlinghaus, Heinrich F.
AU - Dörrer, Lars
AU - Schmidt, Harald
N1 - Funding Information: We gratefully acknowledge financial support from the DFG (Deutsche Forschungs-gemeinschaft, Research Unit FOR1277 molife). We appreciate to Felix Draude for supervising the ToF-SIMS measurements and Marc Krey for ICP-OES measurements.
PY - 2012/6/1
Y1 - 2012/6/1
N2 - Single crystals of titanium disulfide TiS2 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 10mol 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 2nd 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 (cBuLi) was observed, with a corresponding decrease in activation energy from 59.6±7.6 kJmol-1 (cBuLi = 1.6molL-1) to 42.6±11.7 kJmol-1 (cBuLi = 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 Spectrometry) 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 Da/b is at least four orders of magnitude lower than D||a/b.
AB - Single crystals of titanium disulfide TiS2 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 10mol 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 2nd 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 (cBuLi) was observed, with a corresponding decrease in activation energy from 59.6±7.6 kJmol-1 (cBuLi = 1.6molL-1) to 42.6±11.7 kJmol-1 (cBuLi = 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 Spectrometry) 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 Da/b is at least four orders of magnitude lower than D||a/b.
KW - Diffusion
KW - Intercalation
KW - LASER-Ablation Spectrometry
KW - Lithium
UR - http://www.scopus.com/inward/record.url?scp=84862837780&partnerID=8YFLogxK
U2 - 10.1524/zpch.2012.0227
DO - 10.1524/zpch.2012.0227
M3 - Article
AN - SCOPUS:84862837780
VL - 226
SP - 461
EP - 489
JO - Zeitschrift fur Physikalische Chemie
JF - Zeitschrift fur Physikalische Chemie
SN - 0942-9352
IS - 5-6
ER -