TY - JOUR

T1 - Effect of molybdenum disulfide doping with substitutional nitrogen and sulfur vacancies on lithium intercalation

AU - Kotsun, Alena A.

AU - Alekseev, Victor A.

AU - Stolyarova, Svetlana G.

AU - Makarova, Anna A.

AU - Grebenkina, Mariya A.

AU - Zubareva, Anna P.

AU - Okotrub, Alexander V.

AU - Bulusheva, Lyubov G.

N1 - The authors thank Dr. E.A. Maksimovskiy for SEM measurements, Dr. A.V. Ischenko for TEM measurements, Dr. Yu.V. Shubin for XRD data, Dr. E.V. Shlyakhova for Raman spectra, and the Helmholtz-Zentrum Berlin für Materialien und Energie for the allocation of beamtime for XPS measurements. The research was conducted under support of the Ministry of Science and Higher Education of the Russian Federation (project 121031700314-5), the electrochemical studies were founded by the Russian Foundation for Basic Research (Grant 21-53-12021). A.A.M. acknowledges BMBF (grant no. 05K19KER). Публикация для корректировки.

PY - 2023/6/25

Y1 - 2023/6/25

N2 - Molybdenum disulfide (MoS2) nanomaterials were synthesized by rapid decomposition of ammonium tetrathiomolybdate in argon or ammonia at 600 °C and 700 °C. The change of environment had no effect on the morphology, but it affected the composition and electronic structure of the nanomaterial. The use of gaseous NH3 in the synthesis led to the incorporation of nitrogen and the formation of sulfur vacancies in the MoS2 lattice. An electrochemical study showed that this dual lattice modification significantly reduced the irreversible capacity in the first cycle and improved the lithium capacity and structural stability of MoS2 in the voltage range of 2.5–1.1 V. After 65 cycles of the operation of lithium-ion battery, the specific capacity of the defective MoS2 was 189 mAh g–1, which is higher than the theoretical capacity of ideal MoS2. An increase in electrical conductivity and a decrease in charge transfer resistance determined by using electrochemical impedance spectroscopy were associated with a decrease in the band gap in MoS2 due to the substitutional nitrogen atoms and sulfur vacancies, as shown by density functional theory calculations. In addition, these defects create new sites for lithium adsorption and increase the intercalation voltage.

AB - Molybdenum disulfide (MoS2) nanomaterials were synthesized by rapid decomposition of ammonium tetrathiomolybdate in argon or ammonia at 600 °C and 700 °C. The change of environment had no effect on the morphology, but it affected the composition and electronic structure of the nanomaterial. The use of gaseous NH3 in the synthesis led to the incorporation of nitrogen and the formation of sulfur vacancies in the MoS2 lattice. An electrochemical study showed that this dual lattice modification significantly reduced the irreversible capacity in the first cycle and improved the lithium capacity and structural stability of MoS2 in the voltage range of 2.5–1.1 V. After 65 cycles of the operation of lithium-ion battery, the specific capacity of the defective MoS2 was 189 mAh g–1, which is higher than the theoretical capacity of ideal MoS2. An increase in electrical conductivity and a decrease in charge transfer resistance determined by using electrochemical impedance spectroscopy were associated with a decrease in the band gap in MoS2 due to the substitutional nitrogen atoms and sulfur vacancies, as shown by density functional theory calculations. In addition, these defects create new sites for lithium adsorption and increase the intercalation voltage.

KW - DFT calculations

KW - Lithium-ion intercalation

KW - Nanostructured molybdenum disulfide

KW - Nitrogen doping

KW - Sulfur vacancies

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85150336915&origin=inward&txGid=392b5e763c99c9fdcbdf4dd1d6934082

UR - https://www.mendeley.com/catalogue/c5e48838-e938-3f20-8ddb-1989204c24cb/

U2 - 10.1016/j.jallcom.2023.169689

DO - 10.1016/j.jallcom.2023.169689

M3 - Article

VL - 947

JO - Journal of Alloys and Compounds

JF - Journal of Alloys and Compounds

SN - 0925-8388

M1 - 169689

ER -