Synthesis · Metal-organic framework glass stabilizes high-voltage cathodes for efficient lithium-metal batteries

8 structured synthesis routes

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

Complete recipeSource: Main

Route 1: Other

main p.10 · Electrodes preparation

Metal precursorsGlass@NCM-811, Glass@LRMO, Glass@LCO or bare cathode powders

Solvents1-Methyl-2-pyrrolidone (NMP), Sigma-Aldrich

AdditivesCarbon black; PVDF binder

AtmosphereVacuum drying at 110 deg C overnight after coating

Temperature110

Time4 h stirring; overnight drying

Substrate orientationAl foil current collector

Work-upStirred in NMP 4 h, coated onto Al foil by scraper, pressed, vacuum dried

Scalability contextCoin-cell cathode mass loading about 7.0 mg/cm2; electrode diameter 12 mm.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Glass@NCM-811 or control cathode powder	1.0 g in general electrode recipe	main p.10 · Electrodes preparation
Additive	Carbon black	8:1:1 active:carbon:PVDF ratio	main p.10 · Electrodes preparation
Additive	PVDF	8:1:1 active:carbon:PVDF ratio	main p.10 · Electrodes preparation
Solvent	1-Methyl-2-pyrrolidone (NMP)	not specified; stirred 4 h	main p.10 · Electrodes preparation

Complete recipeSource: Main

Route 2: Other

main p.9 · Synthesis of MOF glass coated high-voltage cathodes

Metal precursorsLiCoO2 cathode purchased from Dodochem Co.; Zn-P-dmbIm MOF powder

Linker precursorsdmbIm in Zn-P-dmbIm MOF powder

AtmosphereVacuum during heating

Temperature175

Time0.1667 h grinding; 0.5 h heating

Work-upManual grinding 10 min, vacuum heating 175 deg C 30 min, fast cooling to room temperature

Scalability contextSame route extended to high-voltage LiCoO2.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	LiCoO2 cathode material	2 wt% MOF Glass coating for default sample	main p.9 · Synthesis of MOF glass coated high-voltage cathodes
Other	as-prepared Zn-P-dmbIm MOF powder	2 wt% relative to cathode for default sample	main p.9 · Synthesis of MOF glass coated high-voltage cathodes

Complete recipeSource: Both

Route 3: Other

main p.9 · Synthesis of MOF glass coated high-voltage cathodes

Metal precursorsLRMO cathode purchased from Dodochem Co.; Zn-P-dmbIm MOF powder

Linker precursorsdmbIm in Zn-P-dmbIm MOF powder

AtmosphereVacuum during heating

Temperature175

Time0.1667 h grinding; 0.5 h heating

Work-upManual grinding 10 min, vacuum heating 175 deg C 30 min, fast cooling to room temperature

Scalability contextSame route extended to LRMO and LCO high-voltage cathodes.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	LRMO or LiCoO2 cathode material	2 wt% MOF Glass coating for default sample	main p.9 · Synthesis of MOF glass coated high-voltage cathodes
Other	as-prepared Zn-P-dmbIm MOF powder	2 wt% relative to cathode for default sample	main p.9 · Synthesis of MOF glass coated high-voltage cathodes

Complete recipeSource: Both

Route 4: Other

main p.9 · Synthesis of MOF glass coated high-voltage cathodes

Metal precursorsNCM-811 cathode purchased from Tianjin Lishen Battery Joint-Stock Co.; Zn-P-dmbIm MOF powder

Linker precursorsdmbIm in Zn-P-dmbIm MOF powder

AtmosphereVacuum during heating

Temperature175

Time0.1667 h grinding; 0.5 h heating

Work-upManual grinding 10 min, vacuum heating 175 deg C 30 min, fast cooling to room temperature

Scalability contextSelected 2 wt% as main sample because 5/10 wt% did not improve performance and higher glass loading raises cost and lowers energy density.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	LiNi0.8Co0.1Mn0.1O2 (NCM-811) cathode	weight ratio with MOF powder 2 wt% MOF/NCM-811 for main sample	main p.9 · Synthesis of MOF glass coated high-voltage cathodes
Other	as-prepared Zn-P-dmbIm MOF powder	2 wt% relative to cathode for main sample	main p.9 · Synthesis of MOF glass coated high-voltage cathodes

Complete recipeSource: Both

Route 5: Other

main p.9 · Synthesis of MOF glass

Metal precursorsAs-prepared Zn-P-dmbIm MOF powder

Linker precursorsdmbIm retained from Zn-P-dmbIm MOF powder

AtmosphereVacuum

Temperature175

Time0.5

Work-upFast cooling to room temperature (25 deg C)

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Other	as-prepared Zn-P-dmbIm MOF powder	not specified	main p.9 · Synthesis of MOF glass

Complete recipeSource: Main

Route 6: Other

main p.9 · Synthesis of MOF glass film

Metal precursorsAs-prepared Zn-P-dmbIm MOF powder

Linker precursorsdmbIm retained from Zn-P-dmbIm MOF powder

AtmosphereVacuum

Temperature175

Time0.5

Work-upMechanical pressing into 15 mm pellet at 2 MPa for 60 s, heating, then rapid cooling to room temperature

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Other	as-prepared Zn-P-dmbIm MOF powder	not specified	main p.9 · Synthesis of MOF glass film

Complete recipeSource: Main

Route 7: Other

main p.10 · Cell assembly and electrochemical measurements

Metal precursorsGlass@NCM-811 cathode and limited Li metal anode

SolventsTypical carbonate electrolyte 1 mol/L LiPF6-EC/DMC; 2.6 g

AdditivesCarbon black and PVDF at 9:0.5:0.5 for pouch cathode

AtmosphereArgon-filled glove box; <1 ppm moisture and oxygen

Temperature25

Substrate orientationPouch-cell stack under about 10 MPa external pressure

Work-upCR2032/coin-like preparation adapted to pouch; 4.5 x 9.5 cm2 separator; constrained steel enclosure

ActivationCells kept open-circuit 16 h before electrochemical characterization

Scalability context2.0 Ah-level pouch; low E/C ratio 1.3 g Ah-1; whole pouch-cell mass 19.579 g.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Electrolyte	1 mol/L LiPF6-EC/DMC	2.6 g for pouch cell · 1 mol/L	main p.10 · Cell assembly and electrochemical measurements
Other	Glass@NCM-811 cathode	31.8 mg/cm2 coated cathode, 28.0 mg/cm2 NCM-811	main p.10 · Cell assembly and electrochemical measurements
Other	lithium metal anode	limited Li, N/P ratio about 3.9:1	main p.10 · Cell assembly and electrochemical measurements

Complete recipeSource: Both

Route 8: Other

main p.9 · Preparation of Zn-P-dmbIm MOF powder

Metal precursorsZn(OAc)2.2H2O (439 mg, 2 mmol, Sigma-Aldrich)

Linker precursors5,6-dimethylbenzimidazole (584.8 mg, 4 mmol, Sigma-Aldrich)

SolventsDichloromethane wash

AdditivesPhosphoric acid (420 uL, 6 mmol, Sigma-Aldrich)

AtmosphereNot specified during grinding/drying

Temperature70

Time0.25 h grinding; 10 h drying

Work-upManual grinding 15 min; washed with dichloromethane three times

ActivationDried at 70 deg C for 10 h

Scalability contextMain text describes this as simple, cost-effective and time-efficient.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Zn(OAc)2.2H2O	439 mg, 2 mmol	main p.9 · Preparation of Zn-P-dmbIm MOF powder
Linker	5,6-dimethylbenzimidazole	584.8 mg, 4 mmol	main p.9 · Preparation of Zn-P-dmbIm MOF powder
Acid	phosphoric acid	420 uL, 6 mmol	main p.9 · Preparation of Zn-P-dmbIm MOF powder
Solvent	dichloromethane	washed three times	main p.9 · Preparation of Zn-P-dmbIm MOF powder