Revealing the Flexible 1D Primary and Globular Secondary Structures of Sulfur-Rich Amorphous Transition Metal Polysulfides

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Revealing the Flexible 1D Primary and Globular Secondary Structures of Sulfur-Rich Amorphous Transition Metal Polysulfides. / Artemkina, Sofya B.; Enyashin, Andrey N.; Poltarak, Anastassiia A. et al.

In: ChemNanoMat, Vol. 5, No. 12, 01.12.2019, p. 1488-1497.

Research output: Contribution to journal › Article › peer-review

BibTeX

@article{a078ceb64cf3428d96bc83be8c320f90,

title = "Revealing the Flexible 1D Primary and Globular Secondary Structures of Sulfur-Rich Amorphous Transition Metal Polysulfides",

abstract = "Sulfur-rich transition metal polysulfides MS5 (M=Mo, W) are synthesized by a low-temperature solution method from corresponding carbonyls M(CO)6 and elemental sulfur. Extensive characterization reveals that all sulfur atoms are assembled into disulfide ligands (S−S) within the structure of the amorphous spherical particles. Their thermodynamic stabilities are estimated for the first time using density functional theory (DFT) calculations, indicating two stable chain models composed either of binuclear [M2S8] or trinuclear [M3S12] fragments linked through S−S units. Molecular dynamics (MD) DFTB simulation proves that the S−S bridges predetermine the supreme flexibility of the polysulfide chains as primary structures of MS5 and their globular secondary arrangements. Interestingly, this type of structural organization is reminiscent of that for classical polymers. Thus, the reasons for MS5 forming exclusively as amorphous phases are uncovered, which may be extended to many other sulfur-rich polysulfides. The potential of these materials as increased capacity cathodes for lithium-ion batteries is shown.",

keywords = "ab initio calculations, amorphous materials, chain structures, molecular dynamics, synthesis design, REDUCED GRAPHENE OXIDE, ROOM-TEMPERATURE, CRYSTAL-STRUCTURE, MOS3, PERFORMANCE, POSITIVE-ELECTRODE, NIOBIUM SULFIDES, MOLYBDENUM SULFIDE, TRISULFIDE, ELECTRONIC-STRUCTURE",

author = "Artemkina, {Sofya B.} and Enyashin, {Andrey N.} and Poltarak, {Anastassiia A.} and Fedorenko, {Anastasiya D.} and Makarova, {Anna A.} and Poltarak, {Pavel A.} and Shin, {Eon Ji} and Hwang, {Seong Ju} and Kim, {Sung Jin} and Grayfer, {Ekaterina D.} and Fedorov, {Vladimir E.}",

note = "Publisher Copyright: {\textcopyright} 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2019",

month = dec,

day = "1",

doi = "10.1002/cnma.201900526",

language = "English",

volume = "5",

pages = "1488--1497",

journal = "ChemNanoMat",

issn = "2199-692X",

publisher = "Wiley-VCH Verlag",

number = "12",

}

RIS

TY - JOUR

T1 - Revealing the Flexible 1D Primary and Globular Secondary Structures of Sulfur-Rich Amorphous Transition Metal Polysulfides

AU - Artemkina, Sofya B.

AU - Enyashin, Andrey N.

AU - Poltarak, Anastassiia A.

AU - Fedorenko, Anastasiya D.

AU - Makarova, Anna A.

AU - Poltarak, Pavel A.

AU - Shin, Eon Ji

AU - Hwang, Seong Ju

AU - Kim, Sung Jin

AU - Grayfer, Ekaterina D.

AU - Fedorov, Vladimir E.

PY - 2019/12/1

Y1 - 2019/12/1

N2 - Sulfur-rich transition metal polysulfides MS5 (M=Mo, W) are synthesized by a low-temperature solution method from corresponding carbonyls M(CO)6 and elemental sulfur. Extensive characterization reveals that all sulfur atoms are assembled into disulfide ligands (S−S) within the structure of the amorphous spherical particles. Their thermodynamic stabilities are estimated for the first time using density functional theory (DFT) calculations, indicating two stable chain models composed either of binuclear [M2S8] or trinuclear [M3S12] fragments linked through S−S units. Molecular dynamics (MD) DFTB simulation proves that the S−S bridges predetermine the supreme flexibility of the polysulfide chains as primary structures of MS5 and their globular secondary arrangements. Interestingly, this type of structural organization is reminiscent of that for classical polymers. Thus, the reasons for MS5 forming exclusively as amorphous phases are uncovered, which may be extended to many other sulfur-rich polysulfides. The potential of these materials as increased capacity cathodes for lithium-ion batteries is shown.

AB - Sulfur-rich transition metal polysulfides MS5 (M=Mo, W) are synthesized by a low-temperature solution method from corresponding carbonyls M(CO)6 and elemental sulfur. Extensive characterization reveals that all sulfur atoms are assembled into disulfide ligands (S−S) within the structure of the amorphous spherical particles. Their thermodynamic stabilities are estimated for the first time using density functional theory (DFT) calculations, indicating two stable chain models composed either of binuclear [M2S8] or trinuclear [M3S12] fragments linked through S−S units. Molecular dynamics (MD) DFTB simulation proves that the S−S bridges predetermine the supreme flexibility of the polysulfide chains as primary structures of MS5 and their globular secondary arrangements. Interestingly, this type of structural organization is reminiscent of that for classical polymers. Thus, the reasons for MS5 forming exclusively as amorphous phases are uncovered, which may be extended to many other sulfur-rich polysulfides. The potential of these materials as increased capacity cathodes for lithium-ion batteries is shown.

KW - ab initio calculations

KW - amorphous materials

KW - chain structures

KW - molecular dynamics

KW - synthesis design

KW - REDUCED GRAPHENE OXIDE

KW - ROOM-TEMPERATURE

KW - CRYSTAL-STRUCTURE

KW - MOS3

KW - PERFORMANCE

KW - POSITIVE-ELECTRODE

KW - NIOBIUM SULFIDES

KW - MOLYBDENUM SULFIDE

KW - TRISULFIDE

KW - ELECTRONIC-STRUCTURE

UR - http://www.scopus.com/inward/record.url?scp=85074439719&partnerID=8YFLogxK

U2 - 10.1002/cnma.201900526

DO - 10.1002/cnma.201900526

M3 - Article

AN - SCOPUS:85074439719

VL - 5

SP - 1488

EP - 1497

JO - ChemNanoMat

JF - ChemNanoMat

SN - 2199-692X

IS - 12

ER -

ID: 22078072