Synthesis · Catalytic Metal-Organic Framework-Functionalized Inverse-Opal Architectured Polymeric Separator for High-Performance Li-S Batteries

10 structured synthesis routes

Completeness describes how fully the route could be reconstructed from the main article and supporting information.

Complete recipeSource: SI

Route 1: Other

5-6 · Experimental section 1.10

Metal precursorsLi foil anode

Linker precursorsrGO/S cathode and ZIF-PIO separator

SolventsDME/DOL electrolyte

AdditivesLiTFSI, LiNO3

Atmosphereargon-filled glove box, water and oxygen below 0.1 ppm

Temperature25 rest after sealing

Time12 rest before testing

Substrate orientationCR2032 coin cell stack with rGO/S cathode, separator and Li foil anode

Work-upSealed CR2032 cells kept for 12 h at 25 deg C before electrochemical testing.

Activationinitial few cycles at low current density for cycling tests

Scalability contextApplication cell assembly, not bulk synthesis.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	rGO/S cathode	thickness around 100 um	5-6 · Experimental section 1.10
Other	Li foil	anode	5-6 · Experimental section 1.10
Other	ZIF-PIO separator	Not specified	5-6 · Experimental section 1.10
Electrolyte	LiTFSI	1 M	5-6 · Experimental section 1.10
Additive	LiNO3	0.1 M	5-6 · Experimental section 1.10
Solvent	DME/DOL	electrolyte-to-S ratio 20 uL mg-1 · 1:1 v/v	5-6 · Experimental section 1.10

Complete recipeSource: SI

Route 2: Other

Experimental section 1.2

Linker precursors4,4-difluorobenzophenone and aniline

Solventstoluene; MeOH recrystallisation

Additives3 A molecular sieves

Atmospherenitrogen

Temperature140

Time24

Work-upToluene and excess aniline removed by rotary evaporation; recrystallised twice from MeOH.

Scalability contextLarge gram-scale monomer quantities reported.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	4,4-DFBP	109.1 g	Experimental section 1.2
Linker	aniline	74.5 g	Experimental section 1.2
Solvent	toluene	400 mL	Experimental section 1.2
Additive	3 A molecular sieves	300 g	Experimental section 1.2
Solvent	MeOH	recrystallisation solvent	Experimental section 1.2

Complete recipeSource: SI

Route 3: Other

5 · Experimental section 1.9

Linker precursorsLi2S and sulfur

SolventsDME/DOL (1:1 v/v) containing 1 M LiTFSI

Atmospherenot stated

Temperature80

Time72

Work-upStirred for homogenisation; concentration adjusted to 0.02 M Li2S6.

Activationnone

Scalability contextSmall-volume model electrolyte preparation.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Li2S	18.38 mg	5 · Experimental section 1.9
Other	sulfur	64 mg	5 · Experimental section 1.9
Solvent	DME/DOL	20 mL · 1:1 v/v	5 · Experimental section 1.9
Electrolyte	LiTFSI	1 M	5 · Experimental section 1.9

Partial recipeSource: SI

Route 4: Other

5,8 · Experimental sections 1.9 and 1.18

Linker precursorsLi2S and sulfur

SolventsDME/DOL or DOL:DME electrolyte containing LiTFSI

Atmospherenot stated

Temperature80 for SI 1.9 solution; not stated for 24 h nucleation-test solution

Time72 for SI 1.9 solution; 24 for nucleation-test solution

Work-upStirred to form Li2S8 solution; used in nucleation/dissolution tests.

Activationnone

Scalability contextModel electrolyte preparation.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Li2S	18.38 mg in analogous SI 1.9 procedure; molar ratio 1:7 in SI 1.18	5,8 · Experimental sections 1.9 and 1.18
Other	sulfur	89.6 mg in SI 1.9; molar ratio with Li2S 1:7 in SI 1.18	5,8 · Experimental sections 1.9 and 1.18
Solvent	DME/DOL or DOL:DME	20 mL for SI 1.9; not stated for SI 1.18 · 1:1 v/v	5,8 · Experimental sections 1.9 and 1.18
Electrolyte	LiTFSI	1 M	5,8 · Experimental sections 1.9 and 1.18

Complete recipeSource: SI

Route 5: Other

Experimental section 1.3

Linker precursorsDFPKt and hydroquinone

SolventsDMAc, toluene, IPA

Additivesdried K2CO3

AtmosphereN2

Temperature140 then 165; dry 120

Time3 at 140; 12 at 165; dry 12

Work-upCool, filter salt byproduct, coagulate in IPA overnight, dry under high vacuum.

Scalability contextGram-scale precursor synthesis.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	DFPKt	8.8 g	Experimental section 1.3
Linker	hydroquinone (HQ)	3.3 g	Experimental section 1.3
Solvent	DMAc	60 mL	Experimental section 1.3
Solvent	toluene	30 mL	Experimental section 1.3
Base	dried K2CO3	5.0 g	Experimental section 1.3
Solvent	IPA	200 mL	Experimental section 1.3

Complete recipeSource: Both

Route 6: Other

Experimental section 1.6

Linker precursorsPEEKt precursor; PS@SiO2 template

SolventsDI water/ethanol 50:50, DMAc, HF solution, toluene, H2SO4

AdditivesPS@SiO2 colloidal particles

Atmosphereslightly reduced pressure during bake; otherwise not stated

Temperatureroom temperature; steam not quantified

TimeH2SO4 steam 12

Substrate orientationglass substrate pretreated with plasma for 1 min

Work-upDissolve particles with 1% HF and toluene, detach film, acid steam conversion of PEEKt to PEEK.

ActivationO2 plasma etching of underside for 3 or 5 min for PIO-3/PIO-5.

Scalability contextSelf-supporting membrane produced by hard-template method.

Show 7 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	PS@SiO2 colloidal particles	15 wt% dispersion	Experimental section 1.6
Solvent	DI water/ethanol	50:50 v/v	Experimental section 1.6
Other	PEEKt precursor	0.1 g	Experimental section 1.6
Solvent	DMAc	50 mL	Experimental section 1.6
Acid	hydrofluoric acid solution	1%	Experimental section 1.6
Solvent	toluene	Not specified	Experimental section 1.6
Acid	H2SO4	1 M	Experimental section 1.6

Complete recipeSource: SI

Route 7: Other

Experimental section 1.4

Linker precursorsstyrene monomer

Solventsethanol and DI water

AdditivesPVP, APS

Atmospherenot stated

Temperature70

Time12

Oxidant / reductantAPS initiator

Work-upWashed with ethanol, centrifuged three times, size-separated by 1 um syringe filter.

Scalability contextColloidal template synthesis.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Additive	PVP	0.06 g	Experimental section 1.4
Solvent	ethanol	150 mL	Experimental section 1.4
Oxidant	APS	0.039 g	Experimental section 1.4
Solvent	DI water	18 mL	Experimental section 1.4
Other	styrene monomer	2.2 mL	Experimental section 1.4

Complete recipeSource: SI

Route 8: Other

Experimental section 1.5

Linker precursorsVTMS silane precursor on PS particles

SolventsDI water, ethanol

Additivesammonia water

Atmosphereambient/not stated

Temperatureroom temperature

Time5

Work-upRepeated centrifugation at 3000 rpm and ultrasonic dispersion in ethanol.

Scalability contextModified Stober process for core-shell template particles.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	VTMS	0.2 mL	Experimental section 1.5
Solvent	DI water	6.8 mL	Experimental section 1.5
Other	PS particles	15 mL · 1 wt%	Experimental section 1.5
Base	ammonia water	0.8 mL	Experimental section 1.5

Complete recipeSource: SI

Route 9: Hydrothermal

Experimental section 1.8

Linker precursorsgraphite, sulfur

SolventsH2SO4/H3PO4, H2O2, DI water

AdditivesKMnO4, carbon black, PVDF

Atmospherenot stated

Temperature20 for GO oxidation; 200 autoclave; oven dry not specified

Time48 h oxidation; 6 h rGO hydrogel; 6 h S/rGO autoclave; 48 h lyophilisation

Substrate orientationAl foil current collector

Oxidant / reductantKMnO4 oxidation; H2O2 quench

Work-upCentrifuge and wash five times, lyophilise, ball-mill, slurry cast on Al foil and oven-dry.

Activationnone stated

Scalability contextApplication cathode preparation.

Show 7 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	graphite	0.5 g	Experimental section 1.8
Oxidant	KMnO4	1 g	Experimental section 1.8
Acid	concentrated H2SO4/H3PO4	50 mL · 9:1 v/v	Experimental section 1.8
Reductant	H2O2	Not specified	Experimental section 1.8
Other	sulfur	3:7 mass ratio with rGO	Experimental section 1.8
Other	carbon black	Not specified	Experimental section 1.8
Other	PVDF	Not specified	Experimental section 1.8

Complete recipeSource: Both

Route 10: Other

Experimental section 1.7

Metal precursorscobalt(II) nitrate

Linker precursors2-methylimidazole

SolventsDI water; isopropyl alcohol rinse; ethylenediamine, glutaraldehyde and histamine solutions

Additivesethylenediamine, glutaraldehyde, histamine

Atmospherenitrogen drying; air dry at room temperature after growth

Temperature125 for ethylenediamine modification; room temperature for MOF growth

Time3 h ethylenediamine; 1 h GA; 1 h histamine; 0.5 h MOF growth

Substrate orientationPIO membrane immersed/soaked sequentially

Work-upRinse with DI water and isopropyl alcohol after ethylenediamine; rinse DI water after GA, histamine and MOF growth; nitrogen blow-dry; air dry.

Activationnone reported after MOF growth

Scalability contextSolution processing on self-supporting membrane; no roll-to-roll scalability tested.

Show 7 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	ethylenediamine	10 mL	Experimental section 1.7
Additive	glutaraldehyde solution	5 mL · 3 w%	Experimental section 1.7
Additive	histamine solution	5 mL · 10 mg mL-1	Experimental section 1.7
Metal Source	Co(NO3)2	11.6 mg mL-1	Experimental section 1.7
Linker	2-methylimidazole (2mIm)	13.1 mg mL-1	Experimental section 1.7
Solvent	DI water	Not specified	Experimental section 1.7
Solvent	isopropyl alcohol	Not specified	Experimental section 1.7