Synthesis · Multiscale optimization of Li-ion diffusion in solid lithium metal batteries: Via ion conductive metal-organic frameworks

16 structured synthesis routes

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

Complete recipeSource: Both

Route 1: Drop Cast

p003 / SI page 3 · Preparation of LCMOF/PVDF-HFP/Li-IL solid electrolyte

Metal precursorsLCMOF-1

Linker precursorsLCMOF-1 framework plus PVDF-HFP

SolventsDMF for PVDF-HFP solution; PC for activation

AdditivesLi-IL; PVDF-HFP

Atmosphereargon glove box storage (<=1 ppm H2O and O2); vacuum drying

Temperature60

Time24

Work-upLCMOF and Li-IL stirred, PVDF-HFP/DMF solution added, stirred 24 h, cast on cleaned petri dishes, prebaked 0.5 h under infrared lamp, dried at 60 deg C under vacuum 12 h, stored in argon glove box.

Activationactivated in 1 M LiTFSI/PC for 2 min and dried

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	LCMOF-1	varied; optimum 70% of LCMOF-1 + PVDF-HFP solids	p003 / SI page 3 · Preparation of LCMOF/PVDF-HFP/Li-IL solid electrolyte
Electrolyte	Li-IL	0.25 or 0.5 mL per 1 g LCMOF-1 tested	p003 / SI page 3 · Preparation of LCMOF/PVDF-HFP/Li-IL solid electrolyte
Other	PVDF-HFP	30% of LCMOF-1 + PVDF-HFP solids · 75 mg/mL in DMF	p003 / SI page 3 · Preparation of LCMOF/PVDF-HFP/Li-IL solid electrolyte
Solvent	DMF	as PVDF-HFP solution solvent	p003 / SI page 3 · Preparation of LCMOF/PVDF-HFP/Li-IL solid electrolyte
Electrolyte	LiTFSI	574.18 mg for Li-IL; 1 M PC activation solution	p003 / SI page 3 · Preparation of LCMOF/PVDF-HFP/Li-IL solid electrolyte
Other	[EMIM][TFSI]	2 mL	p003 / SI page 3 · Preparation of LCMOF/PVDF-HFP/Li-IL solid electrolyte

Complete recipeSource: Both

Route 2: Other

p003 / SI page 3 · Synthesis of LCMOFs

Metal precursorsUiO-66-2CO2H-NDP (100 mg generic MOF basis)

Linker precursorsBDC-2CO2H framework

Solvents1 M LiTFSI in propylene carbonate (15 mL)

AdditivesLiTFSI

Atmospherenot specified

Temperature100

Time6

Work-upMixture kept in shaker for 6 h; solid collected by centrifugation, washed slightly with PC, dried at 100 deg C; pressed into pellets for conductivity.

Activationdried at 100 deg C

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	UiO-66-2CO2H-NDP	100 mg	p003 / SI page 3 · Synthesis of LCMOFs
Electrolyte	LiTFSI	1 M in PC	p003 / SI page 3 · Synthesis of LCMOFs
Solvent	propylene carbonate (PC)	15 mL	p003 / SI page 3 · Synthesis of LCMOFs

Partial recipeSource: Main

Route 3: Other

p004 / 6979 · Results and discussion · Fig. 1e,f

Metal precursorsLCMOF-1

Linker precursorsLCMOF-1 framework plus PVDF-HFP

Solventsnot fully specified for the no-Li-IL 90:10 SE

AdditivesPVDF-HFP

Atmospherenot specified

Work-upManufactured from 90 wt% LCMOF-1 and 10 wt% PVDF-HFP; detailed no-Li-IL membrane casting not separately described.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	LCMOF-1	90 wt%	p004 / 6979 · Results and discussion · Fig. 1e,f
Other	PVDF-HFP	10 wt%	p004 / 6979 · Results and discussion · Fig. 1e,f

Complete recipeSource: Both

Route 4: Drop Cast

p006 / 6981 · Results and discussion · Fig. 4h

Metal precursorsLCMOF-2

Linker precursorsLCMOF-2 framework plus PVDF-HFP

SolventsDMF; PC activation solution

AdditivesLi-IL; PVDF-HFP

Atmosphereargon glove box storage; vacuum drying

Temperature60

Time24

Work-upSame LCMOF/PVDF-HFP/Li-IL membrane casting, drying, storage and activation sequence applied to LCMOF-2 composite SE.

Activationactivated in 1 M LiTFSI/PC for 2 min and dried

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	LCMOF-2	Not specified	p006 / 6981 · Results and discussion · Fig. 4h
Other	PVDF-HFP	75 mg/mL in DMF	p006 / 6981 · Results and discussion · Fig. 4h
Electrolyte	Li-IL	Not specified	p006 / 6981 · Results and discussion · Fig. 4h

Complete recipeSource: SI

Route 5: Other

p003 / SI page 3 · Synthesis of LCMOFs

Metal precursorsUiO-66-SO3H (100 mg generic MOF basis)

Linker precursorsSO3H-functionalised UiO-66 framework

Solvents1 M LiTFSI in PC (15 mL)

AdditivesLiTFSI

Atmospherenot specified

Temperature100

Time6

Work-upSolid collected by centrifugation, washed slightly with PC, dried at 100 deg C.

Activationdried at 100 deg C

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	UiO-66-SO3H	100 mg generic MOF basis	p003 / SI page 3 · Synthesis of LCMOFs
Electrolyte	LiTFSI	1 M in PC	p003 / SI page 3 · Synthesis of LCMOFs
Solvent	propylene carbonate (PC)	15 mL	p003 / SI page 3 · Synthesis of LCMOFs

Complete recipeSource: Both

Route 6: Drop Cast

p006 / 6981 · Results and discussion · Fig. 4i

Metal precursorsLCMOF-3

Linker precursorsLCMOF-3 framework plus PVDF-HFP

SolventsDMF; PC activation solution

AdditivesLi-IL; PVDF-HFP

Atmosphereargon glove box storage; vacuum drying

Temperature60

Time24

Work-upSame LCMOF/PVDF-HFP/Li-IL membrane casting, drying, storage and activation sequence applied to LCMOF-3 composite SE.

Activationactivated in 1 M LiTFSI/PC for 2 min and dried

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	LCMOF-3	Not specified	p006 / 6981 · Results and discussion · Fig. 4i
Other	PVDF-HFP	75 mg/mL in DMF	p006 / 6981 · Results and discussion · Fig. 4i
Electrolyte	Li-IL	Not specified	p006 / 6981 · Results and discussion · Fig. 4i

Complete recipeSource: SI

Route 7: Other

p003 / SI page 3 · Synthesis of LCMOFs

Metal precursorsUiO-66-2OH (100 mg generic MOF basis)

Linker precursors2OH-functionalised UiO-66 framework

Solvents1 M LiTFSI in PC (15 mL)

AdditivesLiTFSI

Atmospherenot specified

Temperature100

Time6

Work-upSolid collected by centrifugation, washed slightly with PC, dried at 100 deg C.

Activationdried at 100 deg C

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	UiO-66-2OH	100 mg generic MOF basis	p003 / SI page 3 · Synthesis of LCMOFs
Electrolyte	LiTFSI	1 M in PC	p003 / SI page 3 · Synthesis of LCMOFs
Solvent	propylene carbonate (PC)	15 mL	p003 / SI page 3 · Synthesis of LCMOFs

Complete recipeSource: Main

Route 8: Other

p002 / 6977 · Cathode mixture

Metal precursorsCommercial LiFePO4

Solventsnot specified

Additivessuper-P carbon black; PVDF

Atmospherevacuum drying

Temperature60

Time24

Substrate orientationaluminium foil

Work-upLiFePO4, super-P and PVDF milled 8:1:1, coated on aluminium foil, dried under vacuum before cell fabrication.

Activationvacuum drying at 60 deg C for 24 h

Scalability contextactive material loading around 2-3 mg cm-2

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Commercial LiFePO4	8 parts by mass	p002 / 6977 · Cathode mixture
Other	super-P carbon black	1 part by mass	p002 / 6977 · Cathode mixture
Other	PVDF	1 part by mass	p002 / 6977 · Cathode mixture

Complete recipeSource: Both

Route 9: Other

p004 / 6979 · Results and discussion · Fig. 1d

Metal precursorsUiO-66-CO2H (100 mg generic MOF basis)

Linker precursorsBDC-CO2H framework

Solvents1 M LiTFSI in PC (15 mL)

AdditivesLiTFSI

Atmospherenot specified

Temperature100

Time6

Work-upSame generic LCMOF loading: shake, centrifuge, PC wash, dry at 100 deg C; pressed into pellets for EIS.

Activationdried at 100 deg C

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	UiO-66-CO2H	100 mg generic MOF basis	p004 / 6979 · Results and discussion · Fig. 1d
Electrolyte	LiTFSI	1 M in PC	p004 / 6979 · Results and discussion · Fig. 1d
Solvent	propylene carbonate (PC)	15 mL	p004 / 6979 · Results and discussion · Fig. 1d

Complete recipeSource: Both

Route 10: Other

p004 / 6979 · Results and discussion · Fig. 1d

Metal precursorsUiO-66 (100 mg generic MOF basis)

Linker precursorsBDC framework

Solvents1 M LiTFSI in PC (15 mL)

AdditivesLiTFSI

Atmospherenot specified

Temperature100

Time6

Work-upSame generic LCMOF loading: shake, centrifuge, PC wash, dry at 100 deg C; pressed into pellets for EIS.

Activationdried at 100 deg C

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	UiO-66	100 mg generic MOF basis	p004 / 6979 · Results and discussion · Fig. 1d
Electrolyte	LiTFSI	1 M in PC	p004 / 6979 · Results and discussion · Fig. 1d
Solvent	propylene carbonate (PC)	15 mL	p004 / 6979 · Results and discussion · Fig. 1d

Partial recipeSource: SI

Route 11: Drop Cast

p003 / SI page 3 · Preparation of LCMOF/PVDF-HFP/Li-IL solid electrolyte

Metal precursorsnone

Linker precursorsPVDF-HFP

SolventsDMF; PC activation solution

AdditivesLi-IL

Atmosphereargon glove box storage; vacuum drying

Temperature60

Time24

Work-upPrepared by the same membrane process without LCMOF-1: PVDF-HFP/DMF plus Li-IL, cast, infrared prebake, vacuum dry, store in argon glove box.

Activationactivated in 1 M LiTFSI/PC for 2 min and dried

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	PVDF-HFP	75 mg/mL in DMF	p003 / SI page 3 · Preparation of LCMOF/PVDF-HFP/Li-IL solid electrolyte
Electrolyte	Li-IL	prepared from 574.18 mg LiTFSI + 2 mL [EMIM][TFSI]	p003 / SI page 3 · Preparation of LCMOF/PVDF-HFP/Li-IL solid electrolyte
Solvent	DMF	Not specified	p003 / SI page 3 · Preparation of LCMOF/PVDF-HFP/Li-IL solid electrolyte
Solvent	PC	1 M LiTFSI activation solution	p003 / SI page 3 · Preparation of LCMOF/PVDF-HFP/Li-IL solid electrolyte

Complete recipeSource: SI

Route 12: Solvothermal

p002 / SI page 2 · Synthesis of nanoparticles of MOFs

Metal precursorsZrCl4 (0.93 g, 4 mmol)

Linker precursors1,4-benzenedicarboxylic acid (H2BDC, 1.32 g, 8 mmol)

Solventshydrochloric acid (0.67 mL); DMF (24 mL)

Additiveshydrochloric acid

Atmospherenot specified

Temperature220

Time16

Work-upWhite powder collected by centrifuge and washed with DMF and ethanol 3 times.

Activationwashing/drying not otherwise specified

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	ZrCl4	0.93 g, 4 mmol	p002 / SI page 2 · Synthesis of nanoparticles of MOFs
Linker	1,4-benzenedicarboxylic acid (H2BDC)	1.32 g, 8 mmol	p002 / SI page 2 · Synthesis of nanoparticles of MOFs
Acid	hydrochloric acid	0.67 mL	p002 / SI page 2 · Synthesis of nanoparticles of MOFs
Solvent	DMF	24 mL	p002 / SI page 2 · Synthesis of nanoparticles of MOFs

Complete recipeSource: Main

Route 13: Solvothermal

p002 / 6977 · Experimental section

Metal precursorsZrCl4 (116.5 mg, 0.5 mmol)

Linker precursors1,2,4,5-benzenetetracarboxylic acid (121 mg, 0.5 mmol)

Solventsformic acid (7 mL); H2O (3 mL)

Additivesformic acid acts as primary solvent and regulator

Atmospherenot specified

Temperature120

Time3

Work-upWhite powder collected by centrifugation and washed with H2O and ethanol 3 times.

Activationno separate activation reported

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	ZrCl4	116.5 mg, 0.5 mmol	p002 / 6977 · Experimental section
Linker	1,2,4,5-benzenetetracarboxylic acid	121 mg, 0.5 mmol	p002 / 6977 · Experimental section
Solvent	formic acid	7 mL	p002 / 6977 · Experimental section
Solvent	H2O	3 mL	p002 / 6977 · Experimental section

Complete recipeSource: SI

Route 14: Solvothermal

p002 / SI page 2 · Synthesis of nanoparticles of MOFs

Metal precursorsZrCl4 (250 mg, 1.08 mmol)

Linker precursors2,5-dihydroxyterephthalic acid (294 mg, 1.5 mmol)

Solventshydrochloric acid (2 mL); DMF (30 mL)

Additiveshydrochloric acid

Atmospherenot specified

Temperature100

Time12

Work-upPowder collected by centrifuge and washed with DMF and ethanol 3 times.

Activationwashing/drying not otherwise specified

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	ZrCl4	250 mg, 1.08 mmol	p002 / SI page 2 · Synthesis of nanoparticles of MOFs
Linker	2,5-dihydroxyterephthalic acid	294 mg, 1.5 mmol	p002 / SI page 2 · Synthesis of nanoparticles of MOFs
Acid	hydrochloric acid	2 mL	p002 / SI page 2 · Synthesis of nanoparticles of MOFs
Solvent	DMF	30 mL	p002 / SI page 2 · Synthesis of nanoparticles of MOFs

Complete recipeSource: SI

Route 15: Hydrothermal

p003 / SI page 3 · Synthesis of nanoparticles of MOFs

Metal precursorsZrCl4 (1.2 g, 5 mmol)

Linker precursors1,2,4-benzenetetracarboxylic acid (2.2 g, 10 mmol)

Solventsdistilled water (25 mL)

Additivesnone reported

Atmosphereambient/stirred then reflux

Temperature100

Time24

Work-upAfter centrifugation and drying, powder was collected.

Activationdrying after centrifugation

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	ZrCl4	1.2 g, 5 mmol	p003 / SI page 3 · Synthesis of nanoparticles of MOFs
Linker	1,2,4-benzenetetracarboxylic acid	2.2 g, 10 mmol	p003 / SI page 3 · Synthesis of nanoparticles of MOFs
Solvent	distilled water	25 mL	p003 / SI page 3 · Synthesis of nanoparticles of MOFs

Complete recipeSource: SI

Route 16: Solvothermal

p002 / SI page 2 · Synthesis of nanoparticles of MOFs

Metal precursorsZrOCl2.8H2O (1.0 g, 3.1 mmol)

Linker precursorssodium 2,5-dicarboxybenzenesulfonate (BDC-SO3Na, 0.83 g, 3.1 mmol)

Solventsformic acid (11.7 mL); N,N-dimethylacetamide (DMA, 30 mL)

Additivesformic acid

Atmospherenot specified

Temperature150

Time24

Work-upPowder collected after centrifugation and drying.

Activationdrying after centrifugation

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	ZrOCl2.8H2O	1.0 g, 3.1 mmol	p002 / SI page 2 · Synthesis of nanoparticles of MOFs
Linker	sodium 2,5-dicarboxybenzenesulfonate (BDC-SO3Na)	0.83 g, 3.1 mmol	p002 / SI page 2 · Synthesis of nanoparticles of MOFs
Solvent	formic acid	11.7 mL	p002 / SI page 2 · Synthesis of nanoparticles of MOFs
Solvent	N,N-dimethylacetamide (DMA)	30 mL	p002 / SI page 2 · Synthesis of nanoparticles of MOFs