Synthesis · Toward High-Performance Metal–Organic-Framework-Based Quasi-Solid-State Electrolytes: Tunable Structures and Electrochemical Properties

25 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

SI pp.S-4-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Metal precursorsCo(NO3)2.6H2O

Linker precursorsH4DOBDC

SolventsDMF/EtOH/H2O 15:1:1; methanol exchange

AdditivesTEA; ligand/TEA 1:5; ligand/metal salt 1:2.5

Atmosphereargon

Temperatureroom temperature; activation 150

Time2 h; activation 24 h

Work-upCentrifuge at 6000 rpm, redisperse in 50 mL DMF and repeat DMF wash two more times; solvent exchange in methanol or acetone at 50 C for 6 h repeated nine times; dry at 30 C under vacuum overnight.

Activation150 C under vacuum for 24 h; stored under Ar

Scalability contextNanoparticles formed by room-temperature additive-mediated precipitation; pellets made by cold pressing.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Co(NO3)2.6H2O	not restated; follows optimized ligand/metal ratio	SI pp.S-4-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Linker	H4DOBDC	not restated	SI pp.S-4-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Base	TEA	not restated; ligand/TEA 1:5; ligand/metal salt 1:2.5	SI pp.S-4-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Complete recipeSource: SI

Route 2: Other

SI pp.S-4-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Metal precursorsCu(NO3)2.3H2O

Linker precursorsH4DOBDC

SolventsDMF/EtOH/H2O 15:1:1; methanol exchange

AdditivesTEA; ligand/TEA 1:4; ligand/metal salt 1:2.5

Atmosphereair

Temperatureroom temperature; activation 150

Time2 h; activation 24 h

Activation150 C under vacuum for 24 h; stored under Ar

Scalability contextNanoparticles formed by room-temperature additive-mediated precipitation; pellets made by cold pressing.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(NO3)2.3H2O	not restated; follows optimized ligand/metal ratio	SI pp.S-4-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Linker	H4DOBDC	not restated	SI pp.S-4-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Base	TEA	not restated; ligand/TEA 1:4; ligand/metal salt 1:2.5	SI pp.S-4-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Complete recipeSource: SI

Route 3: Other

SI pp.S-4-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Metal precursorsCu(NO3)2.3H2O, 1.5 mmol

Linker precursorsH3BTC, 0.75 mmol

SolventsDMF/EtOH/H2O 15:1:1; acetone exchange

AdditivesTEA, 2.25 mmol; ligand/TEA 1:3; ligand/metal salt 1:2

Atmosphereair

Temperatureroom temperature; solvent exchange 50; activation 170

Time2 h stirring after 2 min dropwise addition; activation 24 h

Work-upCentrifuge, DMF wash repeated two more times; acetone exchange at 50 C for 6 h repeated nine times; dry at 30 C under vacuum overnight.

Activation170 C for 24 h under vacuum

Scalability contextNanoparticles formed by room-temperature additive-mediated precipitation; pellets made by cold pressing.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(NO3)2.3H2O	1.5 mmol	SI pp.S-4-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Linker	H3BTC	0.75 mmol	SI pp.S-4-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Base	TEA	2.25 mmol	SI pp.S-4-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Solvent	DMF/EtOH/H2O	100 mL total · 15:1:1 v/v/v	SI pp.S-4-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Complete recipeSource: SI

Route 4: Other

SI p.S-6 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Metal precursorsactivated MOF particles

Solvents1 M LiTFSI/DME; DME wash

AdditivesLiTFSI guest salt, fivefold excess versus metal centre

Atmosphereargon-filled glove box (H2O<0.5 ppm, O2<0.5 ppm)

Temperature50 then 80; drying 50

Time2 days at 50 C plus 1 day at 80 C; drying 24 h

Work-upCentrifuge at 6000 rpm and wash three times with DME.

ActivationDried at 50 C under vacuum for 24 h unless specified.

Scalability contextNanoparticles formed by room-temperature additive-mediated precipitation; pellets made by cold pressing.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Electrolyte	1 M LiTFSI/DME	certain amount · 1 M	SI p.S-6 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Additive	LiTFSI	five times excess of metal centre	SI p.S-6 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Solvent	DME	wash three times	SI p.S-6 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Complete recipeSource: SI

Route 5: Other

SI pp.S-6-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Metal precursorsLi@MOF particles

SolventsDME added during mixing; removed by drying

AdditivesLi-IL binder = 1 M LiTFSI in Pyr14TFSI

Atmosphereargon-filled glove box (H2O<0.5 ppm, O2<0.5 ppm)

Temperaturedrying 120; pressing room temperature

Timedrying 24 h; pressing time not reported

Work-upMixed powder dried at 120 C under vacuum, ground in mortar, sandwiched between PTFE disks in 16 mm stainless-steel mould, pressed under about 4000 psi.

ActivationNo post-sintering; cold-pressed pellet.

Scalability contextNanoparticles formed by room-temperature additive-mediated precipitation; pellets made by cold pressing.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Electrolyte	Li@MOF particles	weight ratio Li@MOF:Li-IL = 1:1.5	SI pp.S-6-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Electrolyte	Li-IL = 1 M LiTFSI in Pyr14TFSI	according to ratio · 1 M	SI pp.S-6-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Solvent	DME	certain amount	SI pp.S-6-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Complete recipeSource: SI

Route 6: Other

SI p.S-6 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Metal precursorsactivated MOF particles

Solvents1 M LiTFSI/DME; DME wash

AdditivesLiTFSI guest salt, fivefold excess versus metal centre

Atmosphereargon-filled glove box (H2O<0.5 ppm, O2<0.5 ppm)

Temperature50 then 80; drying 50

Time2 days at 50 C plus 1 day at 80 C; drying 24 h

Work-upCentrifuge at 6000 rpm and wash three times with DME.

ActivationDried at 50 C under vacuum for 24 h unless specified.

Scalability contextNanoparticles formed by room-temperature additive-mediated precipitation; pellets made by cold pressing.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Electrolyte	1 M LiTFSI/DME	certain amount · 1 M	SI p.S-6 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Additive	LiTFSI	five times excess of metal centre	SI p.S-6 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Solvent	DME	wash three times	SI p.S-6 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Complete recipeSource: SI

Route 7: Other

SI pp.S-6-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Metal precursorsLi@MOF particles

SolventsDME added during mixing; removed by drying

AdditivesLi-IL binder = 1 M LiTFSI in Pyr14TFSI

Atmosphereargon-filled glove box (H2O<0.5 ppm, O2<0.5 ppm)

Temperaturedrying 120; pressing room temperature

Timedrying 24 h; pressing time not reported

Work-upMixed powder dried at 120 C under vacuum, ground in mortar, sandwiched between PTFE disks in 16 mm stainless-steel mould, pressed under about 4000 psi.

ActivationNo post-sintering; cold-pressed pellet.

Scalability contextNanoparticles formed by room-temperature additive-mediated precipitation; pellets made by cold pressing.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Electrolyte	Li@MOF particles	weight ratio Li@MOF:Li-IL = 1:1.5	SI pp.S-6-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Electrolyte	Li-IL = 1 M LiTFSI in Pyr14TFSI	according to ratio · 1 M	SI pp.S-6-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Solvent	DME	certain amount	SI pp.S-6-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Complete recipeSource: SI

Route 8: Other

SI p.S-6 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Metal precursorsactivated MOF particles

Solvents1 M LiTFSI/DME; DME wash

AdditivesLiTFSI guest salt, fivefold excess versus metal centre

Atmosphereargon-filled glove box (H2O<0.5 ppm, O2<0.5 ppm)

Temperature50 then 80; drying 50

Time2 days at 50 C plus 1 day at 80 C; drying 24 h

Work-upCentrifuge at 6000 rpm and wash three times with DME.

ActivationDried at 50 C under vacuum for 24 h unless specified.

Scalability contextNanoparticles formed by room-temperature additive-mediated precipitation; pellets made by cold pressing.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Electrolyte	1 M LiTFSI/DME	certain amount · 1 M	SI p.S-6 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Additive	LiTFSI	five times excess of metal centre	SI p.S-6 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Solvent	DME	wash three times	SI p.S-6 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Complete recipeSource: SI

Route 9: Other

SI pp.S-6-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Metal precursorsLi@MOF particles

SolventsDME added during mixing; removed by drying

AdditivesLi-IL binder = 1 M LiTFSI in Pyr14TFSI

Atmosphereargon-filled glove box (H2O<0.5 ppm, O2<0.5 ppm)

Temperaturedrying 120; pressing room temperature

Timedrying 24 h; pressing time not reported

Work-upMixed powder dried at 120 C under vacuum, ground in mortar, sandwiched between PTFE disks in 16 mm stainless-steel mould, pressed under about 4000 psi.

ActivationNo post-sintering; cold-pressed pellet.

Scalability contextNanoparticles formed by room-temperature additive-mediated precipitation; pellets made by cold pressing.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Electrolyte	Li@MOF particles	weight ratio Li@MOF:Li-IL = 1:1.5	SI pp.S-6-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Electrolyte	Li-IL = 1 M LiTFSI in Pyr14TFSI	according to ratio · 1 M	SI pp.S-6-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Solvent	DME	certain amount	SI pp.S-6-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Complete recipeSource: SI

Route 10: Other

SI p.S-6 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Metal precursorsactivated MOF particles

Solvents1 M LiTFSI/DME; DME wash

AdditivesLiTFSI guest salt, fivefold excess versus metal centre

Atmosphereargon-filled glove box (H2O<0.5 ppm, O2<0.5 ppm)

Temperature50 then 80; drying 50

Time2 days at 50 C plus 1 day at 80 C; drying 24 h

Work-upCentrifuge at 6000 rpm and wash three times with DME.

ActivationDried at 50 C under vacuum for 24 h unless specified.

Scalability contextNanoparticles formed by room-temperature additive-mediated precipitation; pellets made by cold pressing.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Electrolyte	1 M LiTFSI/DME	certain amount · 1 M	SI p.S-6 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Additive	LiTFSI	five times excess of metal centre	SI p.S-6 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Solvent	DME	wash three times	SI p.S-6 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Complete recipeSource: SI

Route 11: Other

SI pp.S-6-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Metal precursorsLi@MOF particles

SolventsDME added during mixing; removed by drying

AdditivesLi-IL binder = 1 M LiTFSI in Pyr14TFSI

Atmosphereargon-filled glove box (H2O<0.5 ppm, O2<0.5 ppm)

Temperaturedrying 120; pressing room temperature

Timedrying 24 h; pressing time not reported

Work-upMixed powder dried at 120 C under vacuum, ground in mortar, sandwiched between PTFE disks in 16 mm stainless-steel mould, pressed under about 4000 psi.

ActivationNo post-sintering; cold-pressed pellet.

Scalability contextNanoparticles formed by room-temperature additive-mediated precipitation; pellets made by cold pressing.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Electrolyte	Li@MOF particles	weight ratio Li@MOF:Li-IL = 1:1.67	SI pp.S-6-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Electrolyte	Li-IL = 1 M LiTFSI in Pyr14TFSI	according to ratio · 1 M	SI pp.S-6-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Solvent	DME	certain amount	SI pp.S-6-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Complete recipeSource: SI

Route 12: Other

SI p.S-6 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Metal precursorsactivated MOF particles

Solvents1 M LiTFSI/DME; DME wash

AdditivesLiTFSI guest salt, fivefold excess versus metal centre

Atmosphereargon-filled glove box (H2O<0.5 ppm, O2<0.5 ppm)

Temperature50 then 80; drying 50

Time2 days at 50 C plus 1 day at 80 C; drying 24 h

Work-upCentrifuge at 6000 rpm and wash three times with DME.

ActivationDried at 50 C under vacuum for 24 h unless specified.

Scalability contextNanoparticles formed by room-temperature additive-mediated precipitation; pellets made by cold pressing.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Electrolyte	1 M LiTFSI/DME	certain amount · 1 M	SI p.S-6 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Additive	LiTFSI	five times excess of metal centre	SI p.S-6 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Solvent	DME	wash three times	SI p.S-6 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Complete recipeSource: SI

Route 13: Other

SI pp.S-6-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Metal precursorsLi@MOF particles

SolventsDME added during mixing; removed by drying

AdditivesLi-IL binder = 1 M LiTFSI in Pyr14TFSI

Atmosphereargon-filled glove box (H2O<0.5 ppm, O2<0.5 ppm)

Temperaturedrying 120; pressing room temperature

Timedrying 24 h; pressing time not reported

Work-upMixed powder dried at 120 C under vacuum, ground in mortar, sandwiched between PTFE disks in 16 mm stainless-steel mould, pressed under about 4000 psi.

ActivationNo post-sintering; cold-pressed pellet.

Scalability contextNanoparticles formed by room-temperature additive-mediated precipitation; pellets made by cold pressing.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Electrolyte	Li@MOF particles	weight ratio Li@MOF:Li-IL = 1:1.5	SI pp.S-6-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Electrolyte	Li-IL = 1 M LiTFSI in Pyr14TFSI	according to ratio · 1 M	SI pp.S-6-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Solvent	DME	certain amount	SI pp.S-6-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Complete recipeSource: SI

Route 14: Other

SI p.S-6 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Metal precursorsactivated MOF particles

Solvents1 M LiTFSI/DME; DME wash

AdditivesLiTFSI guest salt, fivefold excess versus metal centre

Atmosphereargon-filled glove box (H2O<0.5 ppm, O2<0.5 ppm)

Temperature50 then 80; drying 50

Time2 days at 50 C plus 1 day at 80 C; drying 24 h

Work-upCentrifuge at 6000 rpm and wash three times with DME.

ActivationDried at 50 C under vacuum for 24 h unless specified.

Scalability contextNanoparticles formed by room-temperature additive-mediated precipitation; pellets made by cold pressing.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Electrolyte	1 M LiTFSI/DME	certain amount · 1 M	SI p.S-6 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Additive	LiTFSI	five times excess of metal centre	SI p.S-6 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Solvent	DME	wash three times	SI p.S-6 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Complete recipeSource: SI

Route 15: Other

SI pp.S-6-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Metal precursorsLi@MOF particles

SolventsDME added during mixing; removed by drying

AdditivesLi-IL binder = 1 M LiTFSI in Pyr14TFSI

Atmosphereargon-filled glove box (H2O<0.5 ppm, O2<0.5 ppm)

Temperaturedrying 120; pressing room temperature

Timedrying 24 h; pressing time not reported

Work-upMixed powder dried at 120 C under vacuum, ground in mortar, sandwiched between PTFE disks in 16 mm stainless-steel mould, pressed under about 4000 psi.

ActivationNo post-sintering; cold-pressed pellet.

Scalability contextNanoparticles formed by room-temperature additive-mediated precipitation; pellets made by cold pressing.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Electrolyte	Li@MOF particles	weight ratio Li@MOF:Li-IL = 1:1.5	SI pp.S-6-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Electrolyte	Li-IL = 1 M LiTFSI in Pyr14TFSI	according to ratio · 1 M	SI pp.S-6-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Solvent	DME	certain amount	SI pp.S-6-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Complete recipeSource: SI

Route 16: Other

SI p.S-6 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Metal precursorsactivated MOF particles

Solvents1 M LiTFSI/DME; DME wash

AdditivesLiTFSI guest salt, fivefold excess versus metal centre

Atmosphereargon-filled glove box (H2O<0.5 ppm, O2<0.5 ppm)

Temperature50 then 80; drying 50

Time2 days at 50 C plus 1 day at 80 C; drying 24 h

Work-upCentrifuge at 6000 rpm and wash three times with DME.

ActivationDried at 50 C under vacuum for 24 h unless specified.

Scalability contextNanoparticles formed by room-temperature additive-mediated precipitation; pellets made by cold pressing.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Electrolyte	1 M LiTFSI/DME	certain amount · 1 M	SI p.S-6 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Additive	LiTFSI	five times excess of metal centre	SI p.S-6 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Solvent	DME	wash three times	SI p.S-6 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Complete recipeSource: SI

Route 17: Other

SI pp.S-6-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Metal precursorsLi@MOF particles

SolventsDME added during mixing; removed by drying

AdditivesLi-IL binder = 1 M LiTFSI in Pyr14TFSI

Atmosphereargon-filled glove box (H2O<0.5 ppm, O2<0.5 ppm)

Temperaturedrying 120; pressing room temperature

Timedrying 24 h; pressing time not reported

Work-upMixed powder dried at 120 C under vacuum, ground in mortar, sandwiched between PTFE disks in 16 mm stainless-steel mould, pressed under about 4000 psi.

ActivationNo post-sintering; cold-pressed pellet.

Scalability contextNanoparticles formed by room-temperature additive-mediated precipitation; pellets made by cold pressing.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Electrolyte	Li@MOF particles	weight ratio Li@MOF:Li-IL = 1:1.5	SI pp.S-6-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Electrolyte	Li-IL = 1 M LiTFSI in Pyr14TFSI	according to ratio · 1 M	SI pp.S-6-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Solvent	DME	certain amount	SI pp.S-6-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Complete recipeSource: SI

Route 18: Other

SI p.S-6 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Metal precursorsactivated MOF particles

Solvents1 M LiTFSI/DME; DME wash

AdditivesLiTFSI guest salt, fivefold excess versus metal centre

Atmosphereargon-filled glove box (H2O<0.5 ppm, O2<0.5 ppm)

Temperature50 then 80; drying 50

Time2 days at 50 C plus 1 day at 80 C; drying 24 h

Work-upCentrifuge at 6000 rpm and wash three times with DME.

ActivationDried at 50 C under vacuum for 24 h unless specified.

Scalability contextNanoparticles formed by room-temperature additive-mediated precipitation; pellets made by cold pressing.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Electrolyte	1 M LiTFSI/DME	certain amount · 1 M	SI p.S-6 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Additive	LiTFSI	five times excess of metal centre	SI p.S-6 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Solvent	DME	wash three times	SI p.S-6 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Complete recipeSource: SI

Route 19: Other

SI pp.S-6-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Metal precursorsLi@MOF particles

SolventsDME added during mixing; removed by drying

AdditivesLi-IL binder = 1 M LiTFSI in Pyr14TFSI

Atmosphereargon-filled glove box (H2O<0.5 ppm, O2<0.5 ppm)

Temperaturedrying 120; pressing room temperature

Timedrying 24 h; pressing time not reported

Work-upMixed powder dried at 120 C under vacuum, ground in mortar, sandwiched between PTFE disks in 16 mm stainless-steel mould, pressed under about 4000 psi.

ActivationNo post-sintering; cold-pressed pellet.

Scalability contextNanoparticles formed by room-temperature additive-mediated precipitation; pellets made by cold pressing.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Electrolyte	Li@MOF particles	weight ratio Li@MOF:Li-IL = 1:1	SI pp.S-6-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Electrolyte	Li-IL = 1 M LiTFSI in Pyr14TFSI	according to ratio · 1 M	SI pp.S-6-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Solvent	DME	certain amount	SI pp.S-6-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Complete recipeSource: SI

Route 20: Other

SI pp.S-6-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Metal precursorsLi@MOF particles

SolventsDME added during mixing; removed by drying

AdditivesLi-IL binder = 1 M LiTFSI in Pyr14TFSI

Atmosphereargon-filled glove box (H2O<0.5 ppm, O2<0.5 ppm)

Temperaturedrying 120; pressing room temperature

Timedrying 24 h; pressing time not reported

Work-upMixed powder dried at 120 C under vacuum, ground in mortar, sandwiched between PTFE disks in 16 mm stainless-steel mould, pressed under about 4000 psi.

ActivationNo post-sintering; cold-pressed pellet.

Scalability contextNanoparticles formed by room-temperature additive-mediated precipitation; pellets made by cold pressing.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Electrolyte	Li@MOF particles	weight ratio Li@MOF:Li-IL = 1:1.5	SI pp.S-6-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Electrolyte	Li-IL = 1 M LiTFSI in Pyr14TFSI	according to ratio · 1 M	SI pp.S-6-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Solvent	DME	certain amount	SI pp.S-6-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Complete recipeSource: SI

Route 21: Other

SI pp.S-4-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Metal precursorsMg(NO3)2.6H2O

Linker precursorsH4DOBDC

SolventsDMF/EtOH/H2O 15:1:1; methanol exchange

AdditivesTEA; ligand/TEA 1:12; ligand/metal salt 1:2

Atmosphereair

Temperatureroom temperature; activation 150

Time2 h; activation 24 h

Activation150 C under vacuum for 24 h; stored under Ar

Scalability contextNanoparticles formed by room-temperature additive-mediated precipitation; pellets made by cold pressing.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Mg(NO3)2.6H2O	not restated; follows optimized ligand/metal ratio	SI pp.S-4-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Linker	H4DOBDC	not restated	SI pp.S-4-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Base	TEA	not restated; ligand/TEA 1:12; ligand/metal salt 1:2	SI pp.S-4-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Complete recipeSource: SI

Route 22: Other

SI pp.S-4-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Metal precursorsMnCl2.4H2O

Linker precursorsH4DOBDC

SolventsDMF/EtOH/H2O 15:1:1; methanol exchange

AdditivesTEA; ligand/TEA 1:5; ligand/metal salt 1:2.5

Atmosphereargon

Temperatureroom temperature; activation 150

Time2 h; activation 24 h

Activation150 C under vacuum for 24 h; stored under Ar

Scalability contextNanoparticles formed by room-temperature additive-mediated precipitation; pellets made by cold pressing.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	MnCl2.4H2O	not restated; follows optimized ligand/metal ratio	SI pp.S-4-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Linker	H4DOBDC	not restated	SI pp.S-4-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Base	TEA	not restated; ligand/TEA 1:5; ligand/metal salt 1:2.5	SI pp.S-4-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Complete recipeSource: SI

Route 23: Other

SI pp.S-4-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Metal precursorsZn(NO3)2.6H2O, 1.5 mmol

Linker precursorsH2BDC, 1 mmol

SolventsDMF; acetone exchange

AdditivesTEA, 3 mmol; ligand/TEA 1:3; ligand/metal salt 1:1.5

Atmosphereair

Temperatureroom temperature; solvent exchange 50; activation 170

Time2 h stirring after 2 min dropwise addition; activation 24 h

Work-upCentrifuge, DMF wash repeated two more times; acetone exchange at 50 C for 6 h repeated nine times; dry at 30 C under vacuum overnight.

Activation170 C for 24 h under vacuum

Scalability contextNanoparticles formed by room-temperature additive-mediated precipitation; pellets made by cold pressing.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Zn(NO3)2.6H2O	1.5 mmol	SI pp.S-4-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Linker	H2BDC	1 mmol	SI pp.S-4-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Base	TEA	3 mmol	SI pp.S-4-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Solvent	DMF	100 mL total	SI pp.S-4-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Complete recipeSource: SI

Route 24: Other

SI pp.S-4-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Metal precursorsNi(NO3)2.6H2O

Linker precursorsH4DOBDC

SolventsDMF/EtOH/H2O 15:1:1; methanol exchange

AdditivesTEA; ligand/TEA 1:5; ligand/metal salt 1:2.5

Atmosphereargon

Temperatureroom temperature; activation 150

Time2 h; activation 24 h

Activation150 C under vacuum for 24 h; stored under Ar

Scalability contextNanoparticles formed by room-temperature additive-mediated precipitation; pellets made by cold pressing.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(NO3)2.6H2O	not restated; follows optimized ligand/metal ratio	SI pp.S-4-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Linker	H4DOBDC	not restated	SI pp.S-4-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Base	TEA	not restated; ligand/TEA 1:5; ligand/metal salt 1:2.5	SI pp.S-4-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Complete recipeSource: SI

Route 25: Other

SI pp.S-4-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes

Metal precursorsZn(NO3)2.6H2O, 1.5 mmol

Linker precursorsH4DOBDC, 0.6 mmol

SolventsDMF/EtOH/H2O 15:1:1; 30 mL ligand solution and 70 mL metal solution; methanol exchange

AdditivesTEA, 3 mmol; ligand/TEA 1:5; ligand/metal salt 1:2.5

Atmosphereair

Temperatureroom temperature; solvent exchange 50; activation 150

Time2 h stirring after 2 min dropwise addition; activation 24 h

Activation150 C under vacuum for 24 h in glove-box antechamber; stored under Ar

Scalability contextNanoparticles formed by room-temperature additive-mediated precipitation; pellets made by cold pressing.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Zn(NO3)2.6H2O	1.5 mmol	SI pp.S-4-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Linker	H4DOBDC	0.6 mmol	SI pp.S-4-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Base	triethylamine (TEA)	3 mmol	SI pp.S-4-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes
Solvent	DMF/EtOH/H2O	100 mL total · 15:1:1 v/v/v	SI pp.S-4-S-7 · Synthesis of MOFs, Li@MOFs, and Li@MOF/Li-IL electrolytes