Synthesis · Stabilization of NASICON-Type Electrolyte against Li Anode via an Ionic Conductive MOF-Incorporated Adhesive Interlayer

8 structured synthesis routes

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

Partial recipeSource: SI

Route 1: Other

2-3 · 1.3 Electrochemical measurement

Metal precursorsLi metal anode; commercial LFP cathode active material; SSE

Linker precursorsPVDF and PEO binders/polymer components

Solventsnot specified for blade coating

Additivessuper P, PVDF, PEO, LiTFSI

Atmosphereglove box under argon atmosphere for preparation and assembly

Temperaturecells placed at 60 C for 12 h before test; testing at 60 C

Time12 h temperature equilibration before full-cell test; at least 5 h set-temperature standing generally

Substrate orientationLi anode | SSE | LFP cathode full-cell stack

Oxidant / reductantLi metal anode

Work-upcathode blade coated; cathode film cut into 10 mm discs; Li/SSE/LFP full cell assembled

Activation60 C oven for 12 h before test

Scalability contextCathode solvent and coating/drying details not reported.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	commercial LFP	60 parts by weight · cathode loading around 1.3 mg cm-2	2-3 · 1.3 Electrochemical measurement
Additive	super P	12 parts by weight	2-3 · 1.3 Electrochemical measurement
Other	PVDF	20 parts by weight	2-3 · 1.3 Electrochemical measurement
Other	PEO	8 parts by weight	2-3 · 1.3 Electrochemical measurement
Electrolyte	LiTFSI	included in cathode composition; exact ratio text lists 60:12:20:8 by weight for five components · ratio appears to omit one explicit numeric part for LiTFSI	2-3 · 1.3 Electrochemical measurement

Complete recipeSource: SI

Route 2: Other

1 · 1.1 Material synthesis

Metal precursorscommercial LAGP powder, average particle size 0.3 um, purity 99.9%

Atmospherenot specified for sintering

Temperature950

Time10

Substrate orientationpressed in a die before sintering

Work-uppressed in die; sintered; pellet weight around 0.38 g; final diameter 11 mm and thickness 1.2 mm

Activationnone reported

Scalability contextPellet pressing and sintering of commercial powder; no scale-up discussion.

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Other	commercially available LAGP powder	pellet weight around 0.38 g · average particle size 0.3 um; purity 99.9%	1 · 1.1 Material synthesis

Partial recipeSource: SI

Route 3: Other

1 · 1.1 Material synthesis

Linker precursorsPEO

Solventsacetonitrile inferred from similar route to ZCPL; exact amount not specified

AdditivesLiTFSI; PEO:LiTFSI 8:1 by weight

Atmospherenot specified

Temperaturenot specified; similar to ZCPL drying likely 50 C but not explicitly repeated

Timenot specified

Substrate orientationnot specified

Work-upsynthesized in a similar way to ZCPL

Activationnot specified

Scalability contextControl film route lacks absolute amounts and drying details.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	PEO	PEO:LiTFSI = 8:1	1 · 1.1 Material synthesis
Electrolyte	LiTFSI	PEO:LiTFSI = 8:1	1 · 1.1 Material synthesis

Partial recipeSource: SI

Route 4: Drop Cast

1 · 1.1 Material synthesis

Metal precursorsLAGP pellet

Linker precursorsPEO

Solventsnot specified; similar coating route to ZCPL-LAGP

AdditivesLiTFSI

Atmosphereargon-filled glove box inferred from all procedures in coating paragraph

Temperaturenot specified

Timenot specified

Substrate orientationLAGP pellet coated with MOF-free PEO/LiTFSI slurry

Work-upprepared similarly to ZCPL-LAGP using PEO/LiTFSI slurry instead of ZCPL slurry

Activationnot specified

Scalability contextControl route described by analogy only.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	PEO/LiTFSI slurry	not specified · PEO:LiTFSI = 8:1	1 · 1.1 Material synthesis
Other	as-prepared LAGP pellet	one pellet	1 · 1.1 Material synthesis

Partial recipeSource: SI

Route 5: Other

2-3 · 1.3 Electrochemical measurement

Metal precursorsLi metal discs; ZCPL-LAGP or LAGP SSE

Atmosphereglove box under argon atmosphere

Temperaturecell testing at 60 C; assembly temperature not specified

Timecells stood at set temperature at least 5 h before measurement

Substrate orientationSSE sandwiched between two Li metal discs

Oxidant / reductantLi metal

Work-upsealed within a coin-type cell

Activationtemperature equilibration at set temperature for at least 5 h before measurement

Scalability contextCoin-cell assembly; no Li disc dimensions reported.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Li metal discs	two pieces	2-3 · 1.3 Electrochemical measurement
Other	solid-state electrolyte	one SSE · LAGP or ZCPL-LAGP	2-3 · 1.3 Electrochemical measurement

Partial recipeSource: SI

Route 6: Other

1 · 1.1 Material synthesis

Metal precursors1.2 g ZIF-67 containing Co nodes

Linker precursorsZIF-67 framework linker plus PEO matrix

Solventsacetonitrile, amount not specified

Additives2.4 g PEO; 0.3 g LiTFSI

Atmosphereroom temperature; atmosphere not specified for free film casting

Temperatureroom temperature casting; dried at 50

Timestirred until homogeneous slurry; drying time not specified

Substrate orientationhorizontal Teflon plate

Work-upmagnetically stirred to homogeneous slurry, cast onto Teflon plate, dried at 50 C, acetonitrile removed

Activationdrying at 50 C

Scalability contextSolution casting; no solvent volume, film area, yield, or dry time reported.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Additive	ZIF-67	1.2 g	1 · 1.1 Material synthesis
Other	PEO	2.4 g	1 · 1.1 Material synthesis
Electrolyte	LiTFSI	0.3 g	1 · 1.1 Material synthesis
Solvent	acetonitrile	not specified	1 · 1.1 Material synthesis

Partial recipeSource: SI

Route 7: Drop Cast

1 · 1.1 Material synthesis

Metal precursorsZIF-67 component; LAGP pellet

Linker precursorsZIF-67, PEO

Solventsacetonitrile, amount not specified

AdditivesLiTFSI

Atmosphereargon-filled glove box

Temperatureroom temperature; evaporation temperature not specified

Timenot specified

Substrate orientationas-prepared LAGP pellet immersed in ZCPL slurry then removed with tweezers

Work-upZIF-67, PEO and LiTFSI mixed 4:8:1 by weight in acetonitrile; LAGP pellet dipped; ZCPL-protected pellets formed after acetonitrile evaporation

Activationsolvent evaporation; no further activation reported

Scalability contextManual slurry dipping/coating in glove box; no solvent amount, immersion time, or drying duration reported.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Additive	ZIF-67	4 parts by weight	1 · 1.1 Material synthesis
Other	PEO	8 parts by weight	1 · 1.1 Material synthesis
Electrolyte	LiTFSI	1 part by weight	1 · 1.1 Material synthesis
Solvent	acetonitrile	not specified	1 · 1.1 Material synthesis
Other	as-prepared LAGP pellet	one pellet	1 · 1.1 Material synthesis

Complete recipeSource: SI

Route 8: Other

1 · 1.1 Material synthesis

Metal precursors1.4 g Co(NO3)2.6H2O

Linker precursors3.2 g 2-methyimidazole (source spelling preserved)

Solventsmethanol, 100 mL for each precursor solution

Atmosphereroom-temperature ambient atmosphere not otherwise specified

Temperatureroom temperature

Time24 h after 20 min stirring

Work-upsolutions mixed, stirred 20 min, kept 24 h; product filtered, washed and vacuum dried

Activationvacuum dried; no gas-sorption activation temperature reported

Scalability contextBatch solution synthesis in methanol; no yield or scale-up discussion.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Co(NO3)2.6H2O	1.4 g · dissolved in 100 mL methanol	1 · 1.1 Material synthesis
Linker	2-methyimidazole	3.2 g · dissolved in 100 mL methanol	1 · 1.1 Material synthesis
Solvent	methanol	200 mL total	1 · 1.1 Material synthesis