Synthesis · Synthesis of Tostadas-Shaped Metal-Organic Frameworks for Remitting Capacity Fading of Li-Ion Batteries

13 structured synthesis routes

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

Complete recipeSource: SI

Route 1: Drop Cast

p005-p006 · Electrochemical Measurement

Metal precursorsNi-HITP active material (NHM, NHS, or NHP)

Linker precursorsNi-HITP active material

SolventsN-methylpyrrolidone (NMP)

AdditivesSuper-P carbon; PVDF binder

Atmospherecoin cells assembled in Ar-filled glovebox, H2O/O2 below 0.5 ppm

Temperature110 drying

Time6 drying

Substrate orientation9 um copper foil current collector; pressed at 4.0 ton inch 2; 15 mm disks

Oxidant / reductantLi metal counter/reference; LiPF6 EC/DMC electrolyte for cell testing

Work-upCoated foil pressed and punched into 15 mm circular disks; active mass loading 1.5-2.0 mg.

Activationnone stated

Scalability contextStandard 2032 coin-cell electrode fabrication.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Ni-HITP active material	70 wt%	p005-p006 · Electrochemical Measurement
Additive	Super-P carbon	20 wt%	p005-p006 · Electrochemical Measurement
Additive	polyvinylidene fluoride (PVDF)	10 wt%	p005-p006 · Electrochemical Measurement
Solvent	N-methylpyrrolidone	not specified	p005-p006 · Electrochemical Measurement
Electrolyte	LiPF6 in EC/DMC	EC/DMC 1:2 v/v	p005-p006 · Electrochemical Measurement

Complete recipeSource: SI

Route 2: Other

p003-p004 · Ball milling · Figure S1

Metal precursorspre-synthesised Ni-HITP NHS and NHP fractions

Linker precursorspre-synthesised Ni-HITP NHS and NHP fractions

Solventsnone stated

Additivesnone stated

AtmosphereN2

Temperatureambient milling; not specified

Time15 min grinding; 30 min standing

Substrate orientation50 mL agate jar; 5.0 mm agate ball

Oxidant / reductantnone stated

Work-upBall milled at 400 RPM in SFM-1 mixer mill; stood 30 min.

Activationnone stated

Scalability contextOptimisation route; reagent masses for NHS/NHP mixture not stated.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	NHS	not specified	p003-p004 · Ball milling · Figure S1
Other	NHP	not specified	p003-p004 · Ball milling · Figure S1

Complete recipeSource: SI

Route 3: Other

p003-p004 · Ball milling · Figure S1

Metal precursorspre-synthesised Ni-HITP NHS and NHP fractions

Linker precursorspre-synthesised Ni-HITP NHS and NHP fractions

Solventsnone stated

Additivesnone stated

AtmosphereN2

Temperatureambient milling; not specified

Time30 min grinding; 30 min standing

Substrate orientation50 mL agate jar; 5.0 mm agate ball

Oxidant / reductantnone stated

Work-upBall milled at 400 RPM in SFM-1 mixer mill; stood 30 min.

Activationnone stated

Scalability contextOptimisation route; reagent masses for NHS/NHP mixture not stated.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	NHS	not specified	p003-p004 · Ball milling · Figure S1
Other	NHP	not specified	p003-p004 · Ball milling · Figure S1

Complete recipeSource: Both

Route 4: Other

p003 · Ball milling · Figure S1

Metal precursorspre-synthesised Ni-HITP NHS and NHP fractions

Linker precursorspre-synthesised Ni-HITP NHS and NHP fractions

Solventsnone; dry ball milling after purified NHS/NHP synthesis

Additivesnone stated

AtmosphereN2 protection/purge

Temperatureambient milling; not specified

Time0.5 h grinding plus 0.5 h standing

Substrate orientation50 mL agate jar; 5.0 mm agate ball for best NHM(b)

Oxidant / reductantnone stated

Work-upMixture of synthesised NHS and NHP ball milled in SFM-1 mixer mill at 400 RPM; stood 30 min after grinding.

Activationnone stated after milling

Scalability contextMechanochemical step uses 50 mL agate jar; scale of NHS/NHP mixture not reported.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	NHS	not specified	p003 · Ball milling · Figure S1
Other	NHP	not specified	p003 · Ball milling · Figure S1

Complete recipeSource: SI

Route 5: Other

p003-p004 · Ball milling · Figure S1

Metal precursorspre-synthesised Ni-HITP NHS and NHP fractions

Linker precursorspre-synthesised Ni-HITP NHS and NHP fractions

Solventsnone stated

Additivesnone stated

AtmosphereN2

Temperatureambient milling; not specified

Time45 min grinding; 30 min standing

Substrate orientation50 mL agate jar; 5.0 mm agate ball

Oxidant / reductantnone stated

Work-upBall milled at 400 RPM in SFM-1 mixer mill; stood 30 min.

Activationnone stated

Scalability contextOptimisation route; reagent masses for NHS/NHP mixture not stated.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	NHS	not specified	p003-p004 · Ball milling · Figure S1
Other	NHP	not specified	p003-p004 · Ball milling · Figure S1

Complete recipeSource: SI

Route 6: Other

p003-p004 · Ball milling · Figure S1

Metal precursorspre-synthesised Ni-HITP NHS and NHP fractions

Linker precursorspre-synthesised Ni-HITP NHS and NHP fractions

Solventsnone stated

Additivesnone stated

AtmosphereN2

Temperatureambient milling; not specified

Time15 min grinding; 30 min standing

Substrate orientation50 mL agate jar; 8.0 mm agate ball

Oxidant / reductantnone stated

Work-upBall milled at 400 RPM in SFM-1 mixer mill; stood 30 min.

Activationnone stated

Scalability contextOptimisation route; reagent masses for NHS/NHP mixture not stated.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	NHS	not specified	p003-p004 · Ball milling · Figure S1
Other	NHP	not specified	p003-p004 · Ball milling · Figure S1

Complete recipeSource: SI

Route 7: Other

p003-p004 · Ball milling · Figure S1

Metal precursorspre-synthesised Ni-HITP NHS and NHP fractions

Linker precursorspre-synthesised Ni-HITP NHS and NHP fractions

Solventsnone stated

Additivesnone stated

Atmosphereair during loading; N2 purge

Temperatureambient milling; not specified

Time30 min grinding; 30 min standing

Substrate orientation50 mL agate jar; 8.0 mm agate ball

Oxidant / reductantnone stated

Work-upBall milled at 400 RPM in SFM-1 mixer mill; stood 30 min.

Activationnone stated

Scalability contextOptimisation route; reagent masses for NHS/NHP mixture not stated.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	NHS	not specified	p003-p004 · Ball milling · Figure S1
Other	NHP	not specified	p003-p004 · Ball milling · Figure S1

Complete recipeSource: SI

Route 8: Other

p003-p004 · Ball milling · Figure S1

Metal precursorspre-synthesised Ni-HITP NHS and NHP fractions

Linker precursorspre-synthesised Ni-HITP NHS and NHP fractions

Solventsnone stated

Additivesnone stated

AtmosphereN2

Temperatureambient milling; not specified

Time45 min grinding; 30 min standing

Substrate orientation50 mL agate jar; 8.0 mm agate ball

Oxidant / reductantnone stated

Work-upBall milled at 400 RPM in SFM-1 mixer mill; stood 30 min.

Activationnone stated

Scalability contextOptimisation route; reagent masses for NHS/NHP mixture not stated.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	NHS	not specified	p003-p004 · Ball milling · Figure S1
Other	NHP	not specified	p003-p004 · Ball milling · Figure S1

Complete recipeSource: SI

Route 9: Other

p003-p004 · Ball milling · Figure S1

Metal precursorspre-synthesised Ni-HITP NHS and NHP fractions

Linker precursorspre-synthesised Ni-HITP NHS and NHP fractions

Solventsnone stated

Additivesnone stated

AtmosphereN2

Temperatureambient milling; not specified

Time15 min grinding; 30 min standing

Substrate orientation50 mL agate jar; 12.0 mm agate ball

Oxidant / reductantnone stated

Work-upBall milled at 400 RPM in SFM-1 mixer mill; stood 30 min.

Activationnone stated

Scalability contextOptimisation route; reagent masses for NHS/NHP mixture not stated.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	NHS	not specified	p003-p004 · Ball milling · Figure S1
Other	NHP	not specified	p003-p004 · Ball milling · Figure S1

Complete recipeSource: SI

Route 10: Other

p003-p004 · Ball milling · Figure S1

Metal precursorspre-synthesised Ni-HITP NHS and NHP fractions

Linker precursorspre-synthesised Ni-HITP NHS and NHP fractions

Solventsnone stated

Additivesnone stated

AtmosphereN2

Temperatureambient milling; not specified

Time30 min grinding; 30 min standing

Substrate orientation50 mL agate jar; 5.0 mm agate ball

Oxidant / reductantnone stated

Work-upBall milled at 400 RPM in SFM-1 mixer mill; stood 30 min.

Activationnone stated

Scalability contextOptimisation route; reagent masses for NHS/NHP mixture not stated.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	NHS	not specified	p003-p004 · Ball milling · Figure S1
Other	NHP	not specified	p003-p004 · Ball milling · Figure S1

Complete recipeSource: SI

Route 11: Other

p003-p004 · Ball milling · Figure S1

Metal precursorspre-synthesised Ni-HITP NHS and NHP fractions

Linker precursorspre-synthesised Ni-HITP NHS and NHP fractions

Solventsnone stated

Additivesnone stated

AtmosphereN2

Temperatureambient milling; not specified

Time45 min grinding; 30 min standing

Substrate orientation50 mL agate jar; 5.0 mm agate ball

Oxidant / reductantnone stated

Work-upBall milled at 400 RPM in SFM-1 mixer mill; stood 30 min.

Activationnone stated

Scalability contextOptimisation route; reagent masses for NHS/NHP mixture not stated.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	NHS	not specified	p003-p004 · Ball milling · Figure S1
Other	NHP	not specified	p003-p004 · Ball milling · Figure S1

Complete recipeSource: Both

Route 12: Hydrothermal

p002-p003 · Experimental section

Metal precursorsnickel(II) chloride hexahydrate, 4.6 mg

Linker precursorsHITP.6HCl, 10.4 mg

SolventsDI water; methanol wash

Additivesconcentrated aqueous ammonium hydroxide, 25 wt%, 0.4 mL

Atmospherecapped vial; atmosphere not otherwise specified

Temperature65 for reaction and washes; vacuum dry overnight with temperature not specified for NHP

Time0.5 h linker preheat; 2 h stirred reaction; 13 h ageing; DI water sonication/heating repeated; methanol sonication/heating repeated; overnight drying

Substrate orientationbottom precipitate fraction isolated as NHP

Oxidant / reductantnone stated

Work-upRemaining reaction mixture centrifuged; solid sonicated in 15 mL DI water for 5 min then heated at 65 C for 4 h, repeated with final 15 h heating; powder centrifuged; sonicated in 15 mL methanol for 5 min and heated at 65 C for 5 h; methanol wash repeated.

ActivationVacuum drying overnight

Scalability contextSmall-vial synthesis: 20 mL capped glass vials and milligram-scale reagents.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HITP.6HCl	10.4 mg	p002-p003 · Experimental section
Metal Source	nickel(II) chloride hexahydrate	4.6 mg	p002-p003 · Experimental section
Solvent	distilled water	6 mL + 4 mL reaction; 15 mL workup portions	p002-p003 · Experimental section
Base	concentrated aqueous ammonium hydroxide	0.4 mL · 25 wt.%	p002-p003 · Experimental section
Solvent	methanol (CH3OH)	15 mL workup portions	p002-p003 · Experimental section

Complete recipeSource: Both

Route 13: Hydrothermal

p002 · Experimental section

Metal precursorsnickel(II) chloride hexahydrate, 4.6 mg

Linker precursorsHITP.6HCl, 10.4 mg

SolventsDI water; methanol wash

Additivesconcentrated aqueous ammonium hydroxide, 25 wt%, 0.4 mL

Atmospherecapped vial; atmosphere not otherwise specified

Temperature65 for reaction and washes; 50 vacuum dry

Time0.5 h linker preheat; 2 h stirred reaction; 13 h ageing; 4 h + 15 h water treatment; 5 h + 15 h methanol treatment; overnight drying

Substrate orientationair/liquid floating film fraction isolated as NHS

Oxidant / reductantnone stated

Work-upSupernatant with film separated; heated in 20 mL DI water at 65 C for 4 h with DI rinsing; heated in water at 65 C for 15 h; rinsed with methanol; heated in fresh methanol at 65 C for 5 h; methanol removed; film heated at 65 C for 15 h in fresh methanol.

ActivationVacuum oven at 50 C overnight

Scalability contextSmall-vial synthesis: 20 mL capped glass vials and milligram-scale reagents.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	2,3,6,7,10,11-hexaaminotriphenylene hexahydrochloric acid (HITP.6HCl)	10.4 mg	p002 · Experimental section
Metal Source	nickel(II) chloride hexahydrate	4.6 mg	p002 · Experimental section
Solvent	distilled water	6 mL for linker; 4 mL for nickel solution; 20 mL workup	p002 · Experimental section
Base	concentrated aqueous ammonium hydroxide	0.4 mL · 25 wt.%	p002 · Experimental section
Solvent	methanol (CH3OH)	fresh wash solvent; volume not fully specified	p002 · Experimental section