Catalysing the performance of Li-sulfur batteries with two-dimensional conductive metal organic frameworks

Preeti Bhauriyal; Thomas Heine

doi:10.1039/d2ta00521b

Catalysing the performance of Li-sulfur batteries with two-dimensional conductive metal organic frameworks

Preeti Bhauriyal, Thomas Heine

Department of Chemistry

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

2 Citations (Scopus)

Abstract

At present, the efficiency of high energy density Li-sulfur (Li-S) batteries is being narrowed by the limited strategies to deal with the shuttling effect, sluggish redox kinetics and poor ionic and electron conductivities of cathode hosts. Recently, synthesized triphenylene based two-dimensional conductive metal organic frameworks (2D MOFs) have been observed to hold promising characteristics to overcome the limitations with suitable pore and anchoring sites along with the desired electron conductivity. In this study, we use density functional theory calculations to investigate 2D honeycomb MOFs with hexa-substituted triphenylene linkers with pairs of varying metal ions (Cu, Ni, and Co) and functional groups (N, O, and S) (M₃(2,3,6,7,10,11-hexaiminotriphenylene)₂ (M₃(HITP)₂), M₃(2,3,6,7,10,11-hexahydroxytriphenylene)₂ (M₃(HOTP)₂) and M₃(triphenylene-2,3,6,7,10,11-hexathiol)₂ (M₃(THT)₂)) to be the potential cathode hosts in Li-S batteries and analyse their structure-activity relationship. The detailed study of structural-electronic characteristics followed by analysis of the triangle of catalytic activity concludes that M₃(HOTP)₂ can deliver higher anchoring efficiency, but it suffers from low redox reactivity with high Li diffusion and Li₂S decomposition barriers, whereas M₃(HITP)₂ MOFs appear insubstantial with the possibility of Li polysulfide shuttling due to the lower anchoring. Co₃(THT)₂ not only has superior anchoring efficiency (−1.40 to −2.68 eV) but also shines in terms of facile Li⁺ diffusion (0.68 eV), a small Gibbs free energy requirement of 0.68 eV for Li polysulfide reduction and a moderately low Li₂S decomposition barrier (1.06 eV) that simultaneously contribute to the performance of Li-S batteries. Our study concludes that the combination of Co and S in Co₃(THT)₂ makes the most suitable cathode host and provides a basis for the designing and screening of new materials having such active components to achieve high performance Li-S batteries.

Original language	English
Pages (from-to)	12400-12408
Number of pages	9
Journal	Journal of Materials Chemistry A
Volume	10
Issue number	23
DOIs	https://doi.org/10.1039/d2ta00521b
Publication status	Published - 2022 May 11

Bibliographical note

Funding Information:
We thank the Center for Information Services and High-Performance Computing (ZIH) at TU Dresden for generous allocation of computer time. P. B. acknowledges the Alexander-von-Humboldt Foundation for funding. The authors also thank Deutsche Forschungsgemeinschaft within CRC 1415 for support.

Publisher Copyright:
© 2022 The Royal Society of Chemistry

All Science Journal Classification (ASJC) codes

Chemistry(all)
Renewable Energy, Sustainability and the Environment
Materials Science(all)

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1039/d2ta00521b

Cite this

@article{b059dd8dd842487c87554955809fb2e1,

title = "Catalysing the performance of Li-sulfur batteries with two-dimensional conductive metal organic frameworks",

abstract = "At present, the efficiency of high energy density Li-sulfur (Li-S) batteries is being narrowed by the limited strategies to deal with the shuttling effect, sluggish redox kinetics and poor ionic and electron conductivities of cathode hosts. Recently, synthesized triphenylene based two-dimensional conductive metal organic frameworks (2D MOFs) have been observed to hold promising characteristics to overcome the limitations with suitable pore and anchoring sites along with the desired electron conductivity. In this study, we use density functional theory calculations to investigate 2D honeycomb MOFs with hexa-substituted triphenylene linkers with pairs of varying metal ions (Cu, Ni, and Co) and functional groups (N, O, and S) (M3(2,3,6,7,10,11-hexaiminotriphenylene)2 (M3(HITP)2), M3(2,3,6,7,10,11-hexahydroxytriphenylene)2 (M3(HOTP)2) and M3(triphenylene-2,3,6,7,10,11-hexathiol)2 (M3(THT)2)) to be the potential cathode hosts in Li-S batteries and analyse their structure-activity relationship. The detailed study of structural-electronic characteristics followed by analysis of the triangle of catalytic activity concludes that M3(HOTP)2 can deliver higher anchoring efficiency, but it suffers from low redox reactivity with high Li diffusion and Li2S decomposition barriers, whereas M3(HITP)2 MOFs appear insubstantial with the possibility of Li polysulfide shuttling due to the lower anchoring. Co3(THT)2 not only has superior anchoring efficiency (−1.40 to −2.68 eV) but also shines in terms of facile Li+ diffusion (0.68 eV), a small Gibbs free energy requirement of 0.68 eV for Li polysulfide reduction and a moderately low Li2S decomposition barrier (1.06 eV) that simultaneously contribute to the performance of Li-S batteries. Our study concludes that the combination of Co and S in Co3(THT)2 makes the most suitable cathode host and provides a basis for the designing and screening of new materials having such active components to achieve high performance Li-S batteries.",

author = "Preeti Bhauriyal and Thomas Heine",

note = "Funding Information: We thank the Center for Information Services and High-Performance Computing (ZIH) at TU Dresden for generous allocation of computer time. P. B. acknowledges the Alexander-von-Humboldt Foundation for funding. The authors also thank Deutsche Forschungsgemeinschaft within CRC 1415 for support. Publisher Copyright: {\textcopyright} 2022 The Royal Society of Chemistry",

year = "2022",

month = may,

day = "11",

doi = "10.1039/d2ta00521b",

language = "English",

volume = "10",

pages = "12400--12408",

journal = "Journal of Materials Chemistry A",

issn = "2050-7488",

publisher = "Royal Society of Chemistry",

number = "23",

}

TY - JOUR

T1 - Catalysing the performance of Li-sulfur batteries with two-dimensional conductive metal organic frameworks

AU - Bhauriyal, Preeti

AU - Heine, Thomas

N1 - Funding Information: We thank the Center for Information Services and High-Performance Computing (ZIH) at TU Dresden for generous allocation of computer time. P. B. acknowledges the Alexander-von-Humboldt Foundation for funding. The authors also thank Deutsche Forschungsgemeinschaft within CRC 1415 for support. Publisher Copyright: © 2022 The Royal Society of Chemistry

PY - 2022/5/11

Y1 - 2022/5/11

N2 - At present, the efficiency of high energy density Li-sulfur (Li-S) batteries is being narrowed by the limited strategies to deal with the shuttling effect, sluggish redox kinetics and poor ionic and electron conductivities of cathode hosts. Recently, synthesized triphenylene based two-dimensional conductive metal organic frameworks (2D MOFs) have been observed to hold promising characteristics to overcome the limitations with suitable pore and anchoring sites along with the desired electron conductivity. In this study, we use density functional theory calculations to investigate 2D honeycomb MOFs with hexa-substituted triphenylene linkers with pairs of varying metal ions (Cu, Ni, and Co) and functional groups (N, O, and S) (M3(2,3,6,7,10,11-hexaiminotriphenylene)2 (M3(HITP)2), M3(2,3,6,7,10,11-hexahydroxytriphenylene)2 (M3(HOTP)2) and M3(triphenylene-2,3,6,7,10,11-hexathiol)2 (M3(THT)2)) to be the potential cathode hosts in Li-S batteries and analyse their structure-activity relationship. The detailed study of structural-electronic characteristics followed by analysis of the triangle of catalytic activity concludes that M3(HOTP)2 can deliver higher anchoring efficiency, but it suffers from low redox reactivity with high Li diffusion and Li2S decomposition barriers, whereas M3(HITP)2 MOFs appear insubstantial with the possibility of Li polysulfide shuttling due to the lower anchoring. Co3(THT)2 not only has superior anchoring efficiency (−1.40 to −2.68 eV) but also shines in terms of facile Li+ diffusion (0.68 eV), a small Gibbs free energy requirement of 0.68 eV for Li polysulfide reduction and a moderately low Li2S decomposition barrier (1.06 eV) that simultaneously contribute to the performance of Li-S batteries. Our study concludes that the combination of Co and S in Co3(THT)2 makes the most suitable cathode host and provides a basis for the designing and screening of new materials having such active components to achieve high performance Li-S batteries.

AB - At present, the efficiency of high energy density Li-sulfur (Li-S) batteries is being narrowed by the limited strategies to deal with the shuttling effect, sluggish redox kinetics and poor ionic and electron conductivities of cathode hosts. Recently, synthesized triphenylene based two-dimensional conductive metal organic frameworks (2D MOFs) have been observed to hold promising characteristics to overcome the limitations with suitable pore and anchoring sites along with the desired electron conductivity. In this study, we use density functional theory calculations to investigate 2D honeycomb MOFs with hexa-substituted triphenylene linkers with pairs of varying metal ions (Cu, Ni, and Co) and functional groups (N, O, and S) (M3(2,3,6,7,10,11-hexaiminotriphenylene)2 (M3(HITP)2), M3(2,3,6,7,10,11-hexahydroxytriphenylene)2 (M3(HOTP)2) and M3(triphenylene-2,3,6,7,10,11-hexathiol)2 (M3(THT)2)) to be the potential cathode hosts in Li-S batteries and analyse their structure-activity relationship. The detailed study of structural-electronic characteristics followed by analysis of the triangle of catalytic activity concludes that M3(HOTP)2 can deliver higher anchoring efficiency, but it suffers from low redox reactivity with high Li diffusion and Li2S decomposition barriers, whereas M3(HITP)2 MOFs appear insubstantial with the possibility of Li polysulfide shuttling due to the lower anchoring. Co3(THT)2 not only has superior anchoring efficiency (−1.40 to −2.68 eV) but also shines in terms of facile Li+ diffusion (0.68 eV), a small Gibbs free energy requirement of 0.68 eV for Li polysulfide reduction and a moderately low Li2S decomposition barrier (1.06 eV) that simultaneously contribute to the performance of Li-S batteries. Our study concludes that the combination of Co and S in Co3(THT)2 makes the most suitable cathode host and provides a basis for the designing and screening of new materials having such active components to achieve high performance Li-S batteries.

UR - http://www.scopus.com/inward/record.url?scp=85131336729&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85131336729&partnerID=8YFLogxK

U2 - 10.1039/d2ta00521b

DO - 10.1039/d2ta00521b

M3 - Article

AN - SCOPUS:85131336729

SN - 2050-7488

VL - 10

SP - 12400

EP - 12408

JO - Journal of Materials Chemistry A

JF - Journal of Materials Chemistry A

IS - 23

ER -

Catalysing the performance of Li-sulfur batteries with two-dimensional conductive metal organic frameworks

Abstract

Bibliographical note

All Science Journal Classification (ASJC) codes

UN SDGs

Access to Document

Other files and links

Fingerprint

Cite this