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

13 measurement groups · 49 results

Reported values remain attached to the sample, method, conditions, extraction quality and source location that produced them.

Charge density difference and Bader charge analysis

Co3(HOTP)2 periodic monolayer DFT model · Model

Charge transfer between S8 or Li2Sx species and each modelled 2D MOF surface.

Temperature: 0
Atmosphere: periodic adsorbate-slab model
Geometry: 2D MOF surface adsorption model
Context: Li2Sx/S8 adsorbed on model frameworks
Measurement source: PDF p4-p5 / article p12403-p12404 · 3.2.1 Anchoring of Li2Sx on 2D MOFs · Figure 2c-d

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Li2S2 to Co3(HOTP)2 charge transferMarked as a best value within this paper	1.38 \|e\|	1.38 \|e\|	—	Text Exact Reported	PDF p5 / article p12404 · 3.2.1 Anchoring of Li2Sx on 2D MOFs · Figure 2d; Figure S5
S8-to-MOF charge transfer lower endpoint	0.002-0.04 \|e\|	0.002 \|e\|	range endpoint	Text Range	PDF p5 / article p12404 · 3.2.1 Anchoring of Li2Sx on 2D MOFs · Figure 2d
S8-to-MOF charge transfer upper endpoint	0.002-0.04 \|e\|	0.04 \|e\|	range endpoint	Text Range	PDF p5 / article p12404 · 3.2.1 Anchoring of Li2Sx on 2D MOFs · Figure 2d

DFT optimised structure, magnetic moment and HSE06 electronic band-gap calculation

Density functional theory

Co3(HITP)2 periodic monolayer DFT model · Model

Pristine Co3(HITP)2 monolayer model.

Temperature: 0
Atmosphere: periodic vacuum slab model
Geometry: 2D monolayer periodic cell
Context: pristine model framework
Measurement source: PDF p3 / article p12402 · 3.1 Structural and electronic properties · Table 1

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
electronic band gap	0.24 eV	0.24 eV	—	Table Exact Reported	PDF p3 / article p12402 · 3.1 Structural and electronic properties · Table 1
lattice constant	21.92 A	21.92 Angstrom	—	Table Exact Reported	PDF p3 / article p12402 · 3.1 Structural and electronic properties · Table 1
magnetic moment per unit cell	3 muB per cell	3 muB per cell	—	Table Exact Reported	PDF p3 / article p12402 · 3.1 Structural and electronic properties · Table 1

DFT optimised structure, magnetic moment and HSE06 electronic band-gap calculation

Density functional theory

Co3(HOTP)2 periodic monolayer DFT model · Model

Pristine Co3(HOTP)2 monolayer model.

Temperature: 0
Atmosphere: periodic vacuum slab model
Geometry: 2D monolayer periodic cell
Context: pristine model framework
Measurement source: PDF p3 / article p12402 · 3.1 Structural and electronic properties · Figure 1; Table 1

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
effective electronic band gap	0 eV; half-metallic	0 eV	—	Table Exact Reported	PDF p3 / article p12402 · 3.1 Structural and electronic properties · Table 1
lattice constant	21.51 A	21.51 Angstrom	—	Table Exact Reported	PDF p3 / article p12402 · 3.1 Structural and electronic properties · Table 1
magnetic moment per unit cell	3 muB per cell	3 muB per cell	—	Table Exact Reported	PDF p3 / article p12402 · 3.1 Structural and electronic properties · Table 1
spin-down band gap	0.25 eV	0.25 eV	—	Text Exact Reported	PDF p3 / article p12402 · 3.1 Structural and electronic properties · Figure 1

PBE-D3 band structure and projected density of states calculation

S8 adsorbed Co3(THT)2 periodic DFT model · Model

S8 and Li2S adsorbed Co3(THT)2 monolayers; Fermi energy set to zero.

Temperature: 0
Atmosphere: periodic adsorbate-slab model
Geometry: 2D monolayer adsorption model
Context: guest-loaded Co3(THT)2 adsorption models
Measurement source: SI p5-p6 / S5-S6 · Figure S7 text · Figure S7

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Li2S adsorbed Co3(THT)2 band gap	0.22 eV	0.22 eV	—	Text Exact Reported	SI p5 / S5 · Figure S7 text · Figure S7
retained electronic conductivity after adsorption	small band gaps suggest Co3(THT)2 can retain high electrical conductivity	—	—	Qualitative Qualitative	PDF p7 / article p12406 · 3.3 Triangle of reactivity · Figure S7
S8 adsorbed Co3(THT)2 band gap	0.39 eV	0.39 eV	—	Text Exact Reported	SI p5 / S5 · Figure S7 text · Figure S7
S8 adsorption-induced valence DOS onset	after ca. -0.9 eV region	-0.9 eV	ca.	Text Approximate	SI p5 / S5 · Figure S7 text · Figure S7

DFT optimised structure, magnetic moment and HSE06 electronic band-gap calculation

Density functional theory

Co3(THT)2 periodic monolayer DFT model · Model

Pristine Co3(THT)2 monolayer model.

Temperature: 0
Atmosphere: periodic vacuum slab model
Geometry: 2D monolayer periodic cell
Context: pristine model framework
Measurement source: PDF p3 / article p12402 · 3.1 Structural and electronic properties · Figure 1; Table 1

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
electronic band gap	0.40 eV	0.4 eV	—	Table Exact Reported	PDF p3 / article p12402 · 3.1 Structural and electronic properties · Table 1
lattice constant	23.22 A	23.22 Angstrom	—	Table Exact Reported	PDF p3 / article p12402 · 3.1 Structural and electronic properties · Table 1
magnetic moment per unit cell	3 muB per cell	3 muB per cell	—	Table Exact Reported	PDF p3 / article p12402 · 3.1 Structural and electronic properties · Table 1

DFT average adsorption energy and surface loading calculation

Density functional theory

S8 adsorbed Co3(THT)2 periodic DFT model · Model

S8 molecules allowed to completely cover both sides of the Co3(THT)2 unit-cell surface.

Temperature: 0
Atmosphere: periodic adsorbate-slab model
Geometry: both sides of Co3(THT)2 unit cell
Context: S8-loaded Co3(THT)2 model
Measurement source: SI p6 / S6 · Figure S8 text · Figure S8

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
average adsorption energy for maximum-loading model	-0.47 eV for 10 Li2S adsorbed on both sides of unitcell	-0.47 eV	—	Text Exact Reported	SI p6 / S6 · Figure S8 text · Figure S8
maximum sulfur loading capacityMarked as a best value within this paper	71.8 %	71.8 wt%	—	Text Exact Reported	SI p6 / S6 · Figure S8 text · Figure S8

DFT optimised structure, magnetic moment and HSE06 electronic band-gap calculation

Density functional theory

Cu3(HITP)2 periodic monolayer DFT model · Model

Pristine Cu3(HITP)2 monolayer model.

Temperature: 0
Atmosphere: periodic vacuum slab model
Geometry: 2D monolayer periodic cell
Context: pristine model framework
Measurement source: PDF p3 / article p12402 · 3.1 Structural and electronic properties · Figure 1; Table 1

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
electronic band gap	0 eV; metallic	0 eV	—	Table Exact Reported	PDF p3 / article p12402 · 3.1 Structural and electronic properties · Figure 1; Table 1
lattice constant	22.09 A	22.09 Angstrom	—	Table Exact Reported	PDF p3 / article p12402 · 3.1 Structural and electronic properties · Table 1
magnetic moment per unit cell	0 muB per cell	0 muB per cell	—	Table Exact Reported	PDF p3 / article p12402 · 3.1 Structural and electronic properties · Table 1

VASP periodic spin-polarised DFT; PBE-GGA; PAW; Grimme DFT-D3; CI-NEB for diffusion/decomposition barriers; HSE06 for electronic band gaps in Table 1

Density functional theory

Co3(THT)2 periodic monolayer DFT model · Model

Plane-wave cutoff 520 eV; SCF convergence 1e-5 eV per atom; force convergence below 1e-2 eV Angstrom-1; Monkhorst-Pack meshes 5 x 5 x 1 for optimisation and 15 x 15 x 1 for electronic calculations; 25 Angstrom z-vacuum.

Temperature: 0
Atmosphere: periodic vacuum slab model
Geometry: 2D monolayer periodic cell
Context: applies to all five pristine model frameworks and adsorbed Li2Sx/S8 models
Measurement source: PDF p2 / article p12401 · 2. Computational details

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
plane-wave cutoff energy	520 eV	520 eV	—	Text Exact Reported	PDF p2 / article p12401 · Computational details
vacuum spacing along z	25 A	25 Angstrom	—	Text Exact Reported	PDF p2 / article p12401 · Computational details

DFT Gibbs free energy profile using Norskov model and zero-point-energy correction

Density functional theory

Co3(THT)2 periodic monolayer DFT model · Model

Discharge lithiation sequence S8* -> Li2S8* -> Li2S4* -> Li2S2* -> Li2S* on MOF surfaces; entropy term neglected at 0 K.

Temperature: 0
Atmosphere: periodic adsorbate-slab model
Geometry: 2D MOF surface reaction pathway
Context: Li2Sx/S8 adsorbed on model framework
Measurement source: PDF p6 / article p12405 · 3.2.3.1 Discharging process · Figure 4

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Li2S4@MOF to Li2S2@MOF Gibbs free energy change	-0.99 eV	-0.99 eV	—	Text Exact Reported	PDF p6 / article p12405 · 3.2.3.1 Discharging process · Figure 4
rate-limiting Li polysulfide reduction Gibbs free energyMarked as a best value within this paper	0.68 eV	0.68 eV	—	Text Exact Reported	PDF p6 / article p12405 · 3.2.3.1 Discharging process · Figure 4

CI-NEB Li2S decomposition barrier calculation

Co3(THT)2 periodic monolayer DFT model · Model

Li2S decomposition path Li2S -> LiS + Li+ + e-; direct path-1 and indirect path-2 considered for each MOF, with preferred dissociative path used for barriers.

Temperature: 0
Atmosphere: periodic adsorbate-slab model
Geometry: 2D MOF surface decomposition pathway
Context: Li2S adsorbed on model framework
Measurement source: PDF p6-p7 / article p12405-p12406 · 3.2.3.2 Charging process · Figure 5; Table S1

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Li2S decomposition barrier	1.18 eV	1.18 eV	—	Text Exact Reported	PDF p6 / article p12405 · 3.2.3.2 Charging process · Figure 5; Table S1
Li2S decomposition barrier	1.27 eV	1.27 eV	—	Text Exact Reported	PDF p6 / article p12405 · 3.2.3.2 Charging process · Figure 5; Table S1
Li2S decomposition barrier	1.06 eV	1.06 eV	—	Text Exact Reported	PDF p6 / article p12405 · 3.2.3.2 Charging process · Figure 5; Table S1
Li2S decomposition barrierMarked as a best value within this paper	0.73 eV	0.73 eV	—	Text Exact Reported	PDF p6 / article p12405 · 3.2.3.2 Charging process · Figure 5; Table S1
Li2S decomposition barrier	1.08 eV	1.08 eV	—	Text Exact Reported	PDF p6 / article p12405 · 3.2.3.2 Charging process · Figure 5; Table S1

DFT adsorption energy calculation, Eads = EMOF-Li2Sx - EMOF - ELi2Sx

Density functional theory

Co3(THT)2 periodic monolayer DFT model · Model

Li2Sx species with x = 1, 2, 4, 6, 8 and S8 adsorbed on modelled 2D MOFs; most stable adsorption conformations selected.

Temperature: 0
Atmosphere: periodic adsorbate-slab model
Geometry: 2D MOF surface adsorption model
Context: pristine model framework with Li2Sx/S8 adsorbates
Measurement source: PDF p2-p5 / article p12401-p12404 · Computational details; 3.2.1 Anchoring of Li2Sx on 2D MOFs · Figure 2; Table S1

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Li2S8-Li2S binding energy range, least negative endpoint	-0.85 to -1.98 eV	-0.85 eV	range endpoint	SI Table Range	SI p4 / S4 · Table S1 · Table S1
Li2S8-Li2S binding energy range, most negative endpoint	-0.85 to -1.98 eV	-1.98 eV	range endpoint	SI Table Range	SI p4 / S4 · Table S1 · Table S1
Li2S8-Li2S binding energy range, least negative endpointMarked as a best value within this paper	-1.93 to -3.54 eV	-1.93 eV	range endpoint	SI Table Range	SI p4 / S4 · Table S1 · Table S1
Li2S8-Li2S binding energy range, most negative endpointMarked as a best value within this paper	-1.93 to -3.54 eV	-3.54 eV	range endpoint	SI Table Range	SI p4 / S4 · Table S1 · Table S1
Li2S8-Li2S binding energy range, least negative endpoint	-1.40 to -2.68 eV	-1.4 eV	range endpoint	SI Table Range	SI p4 / S4 · Table S1 · Table S1
Li2S8-Li2S binding energy range, most negative endpoint	-1.40 to -2.68 eV	-2.68 eV	range endpoint	SI Table Range	SI p4 / S4 · Table S1 · Table S1
Li2S8-Li2S binding energy range, least negative endpoint	-1.14 to -1.60 eV	-1.14 eV	range endpoint	SI Table Range	SI p4 / S4 · Table S1 · Table S1
Li2S8-Li2S binding energy range, most negative endpoint	-1.14 to -1.60 eV	-1.6 eV	range endpoint	SI Table Range	SI p4 / S4 · Table S1 · Table S1
Li2S8-Li2S binding energy range, least negative endpoint	-0.98 to -1.44 eV	-0.98 eV	range endpoint	SI Table Range	SI p4 / S4 · Table S1 · Table S1
Li2S8-Li2S binding energy range, most negative endpoint	-0.98 to -1.44 eV	-1.44 eV	range endpoint	SI Table Range	SI p4 / S4 · Table S1 · Table S1

CI-NEB Li+ diffusion barrier calculation

Co3(THT)2 periodic monolayer DFT model · Model

Li atom diffusion from one stable interaction site to a neighbouring site along MOF surface path-1; path-2 through pore also considered.

Temperature: 0
Atmosphere: periodic vacuum slab model
Geometry: 2D MOF surface diffusion pathway
Context: pristine model framework
Measurement source: PDF p5-p6 / article p12404-p12405 · 3.2.2 Diffusivity · Figure 3; Table S1

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Li+ diffusion barrier	0.26 eV	0.26 eV	—	SI Table Exact Reported	SI p4 / S4 · Table S1 · Table S1
Li+ diffusion barrier	1.08 eV	1.08 eV	—	SI Table Exact Reported	PDF p5 / article p12404 · 3.2.2 Diffusivity · Figure 3c; Table S1
Li+ diffusion barrier	0.68 eV	0.68 eV	—	SI Table Exact Reported	SI p4 / S4 · Table S1 · Table S1
Li+ diffusion barrier	0.76 eV	0.76 eV	—	SI Table Exact Reported	PDF p5 / article p12404 · 3.2.2 Diffusivity · Figure 3b; Table S1
Li+ diffusion barrierMarked as a best value within this paper	0.22 eV	0.22 eV	—	SI Table Exact Reported	PDF p5 / article p12404 · 3.2.2 Diffusivity · Figure 3c; Table S1

DFT optimised structure, magnetic moment and HSE06 electronic band-gap calculation

Density functional theory

Ni3(HITP)2 periodic monolayer DFT model · Model

Pristine Ni3(HITP)2 monolayer model.

Temperature: 0
Atmosphere: periodic vacuum slab model
Geometry: 2D monolayer periodic cell
Context: pristine model framework
Measurement source: PDF p3 / article p12402 · 3.1 Structural and electronic properties · Figure 1; Table 1

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
electronic band gap	0.12 eV	0.12 eV	—	Table Exact Reported	PDF p3 / article p12402 · 3.1 Structural and electronic properties · Table 1
lattice constant	21.88 A	21.88 Angstrom	—	Table Exact Reported	PDF p3 / article p12402 · 3.1 Structural and electronic properties · Table 1
magnetic moment per unit cell	0 muB per cell	0 muB per cell	—	Table Exact Reported	PDF p3 / article p12402 · 3.1 Structural and electronic properties · Table 1