Synthesis · Conductive Metal-Organic Framework for High Energy Sodium-Ion Hybrid Capacitors

5 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

2 · 2.1.1 Synthesis of Conductive Ni-Based Metal-Organic Framework

Metal precursorsNi(NO3)2.6H2O (160 mg)

Linker precursorshexaminobenzene trihydrochloride (HAB.3HCl, 60 mg)

Solventsdistilled water; acetone wash

Additivesconcentrated NH3.H2O (1.6 mL); 6 M NH3.H2O wash

Atmosphereopen air

Temperatureroom temperature reaction; 100 C NH3.H2O wash; 100 C vacuum drying

Time0.5 h metal/ammonia pre-stir; 2 h reaction; 3 h vacuum drying

Oxidant / reductantair/O2 implied by open-air oxidative deprotonation; concentrated NH3.H2O base

Work-upFiltered, washed with plenty of distilled water and 6 M NH3.H2O at 100 C, then washed with acetone.

ActivationDried at 100 C for 3 h under vacuum.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(NO3)2.6H2O	160 mg	2 · 2.1.1 Synthesis of Conductive Ni-Based Metal-Organic Framework
Linker	hexaminobenzene trihydrochloride (HAB.3HCl)	60 mg	2 · 2.1.1 Synthesis of Conductive Ni-Based Metal-Organic Framework
Solvent	distilled water	10 mL for Ni solution; 10 mL for HAB.3HCl solution	2 · 2.1.1 Synthesis of Conductive Ni-Based Metal-Organic Framework
Base	concentrated NH3.H2O	1.6 mL · concentrated	2 · 2.1.1 Synthesis of Conductive Ni-Based Metal-Organic Framework
Base	NH3.H2O wash	6 M	2 · 2.1.1 Synthesis of Conductive Ni-Based Metal-Organic Framework
Solvent	acetone	Not specified	2 · 2.1.1 Synthesis of Conductive Ni-Based Metal-Organic Framework

Complete recipeSource: SI

Route 2: Other

S5 · 1.3 Electrochemical quartz crystal microbalance

Solventsdistilled water; ethylene glycol temporary adhesive; acetone bath

Additivescellulose microporous membrane, 0.22 micrometre pore diameter

Atmospherevacuum oven drying after transfer

Temperature80

Time1

Substrate orientation4.95 MHz AT-cut gold quartz sensor electrode

Work-upVacuum filtration of Ni-MOF dispersion, wet transfer of membrane-covered film to quartz sensor, acetone soak for 30 min to dissolve membrane.

ActivationVacuum oven at 80 C for 60 min, then cooled to room temperature.

Scalability contextVFT film-transfer preparation for EQCM sensor, not presented as scalable bulk synthesis.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Ni-MOF powder	0.32 mg	S5 · 1.3 Electrochemical quartz crystal microbalance
Solvent	distilled water	500 mL	S5 · 1.3 Electrochemical quartz crystal microbalance
Additive	ethylene glycol	temporary adhesive	S5 · 1.3 Electrochemical quartz crystal microbalance
Solvent	acetone	bath, 30 min soak	S5 · 1.3 Electrochemical quartz crystal microbalance

Complete recipeSource: SI

Route 3: Drop Cast

S2-S3 · 1.2 Electrochemical measurements

Solventsdistilled water

AdditivesKetjen Black conductive carbon; carboxymethyl cellulose binder

Atmospherevacuum drying; cells assembled in Ar-filled glove box

Temperature60

Time12

Substrate orientationaluminium foil current collector

Work-upHomogeneous slurry cast onto aluminium foil.

ActivationDried at 60 C for 12 h under vacuum; Ni-MOF electrode pre-activated for full-cell testing by three cycles at 50 mA g-1 in Ni-MOF//Na configuration.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Ni-MOF active material	mass ratio 8 parts	S2-S3 · 1.2 Electrochemical measurements
Additive	Ketjen Black (KB)	mass ratio 1 part	S2-S3 · 1.2 Electrochemical measurements
Additive	carboxymethyl cellulose (CMC) binder	mass ratio 1 part	S2-S3 · 1.2 Electrochemical measurements
Solvent	distilled water	Not specified	S2-S3 · 1.2 Electrochemical measurements

Partial recipeSource: Both

Route 4: Drop Cast

2 · 2.1.2

Metal precursorsNVOPF prepared according to previous report; not detailed here

Solventsdistilled water

Additivesactive carbon; Ketjen Black; CMC binder

Atmospherevacuum drying; cells assembled in Ar-filled glove box

Temperature60

Time12

Substrate orientationaluminium foil current collector

Work-upPrepared under same slurry-casting conditions as the Ni-MOF working electrode.

ActivationDried under vacuum; no separate activation reported for NVOPF/AC.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	NVOPF	mass ratio 4 parts	2 · 2.1.2
Additive	active carbon (AC), purchased by Kuraray	mass ratio 4 parts	2 · 2.1.2
Additive	Ketjen Black (KB)	mass ratio 1 part	2 · 2.1.2
Additive	carboxymethyl cellulose (CMC) binder	mass ratio 1 part	2 · 2.1.2

Complete recipeSource: SI

Route 5: Other

S3 · 1.2 Electrochemical measurements · Figure S1

Solvents1 M NaClO4 in EC:PC = 1:1 with 5 vol% FEC electrolyte

Additivesglass microfiber filter separator; sodium metal reference/counter electrode

AtmosphereAr-filled glove box

Temperatureroom temperature testing

Substrate orientationthree-electrode Swagelok cell

Work-upAssembled with Ni-MOF electrode E1 as negative electrode, NVOPF/AC electrode E2 as positive electrode and sodium metal E3 as reference.

ActivationBefore testing, Ni-MOF electrode was pre-activated in Ni-MOF//Na configuration by cycling three times at 50 mA g-1.

Scalability contextLaboratory three-electrode Swagelok device; mass ratio Ni-MOF:AC/NVOPF = 1:3.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Electrolyte	NaClO4 in ethylene carbonate and propylene carbonate with 5% fluoroethylene carbonate	1 M NaClO4; EC:PC = 1:1 vol:vol; 5 vol% FEC	S3 · 1.2 Electrochemical measurements · Figure S1
Other	Ni-MOF electrode	mass loading about 1.5 mg cm-2	S3 · 1.2 Electrochemical measurements · Figure S1
Other	NVOPF/AC electrode	mass loading about 4.5 mg cm-2	S3 · 1.2 Electrochemical measurements · Figure S1
Other	sodium metal foil	Not specified	S3 · 1.2 Electrochemical measurements · Figure S1