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Hypercrosslinked resins as carbon precursors for supercapacitor

electrodes

Euan Bain

Supervisor: Prof. P. J. Hall

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Today's StoryToday's Story

Characterisation Methods DiscussedCharacterisation Methods Discussed

NN22 Adsorption @ 77K Adsorption @ 77K

Small Angle Neutron Scattering (SANS)Small Angle Neutron Scattering (SANS)

Contrast Matched Small Angle Neutron Contrast Matched Small Angle Neutron Scattering (CM-SANS)Scattering (CM-SANS)

Raw Materials

Gel-Type Resin

Hypercrosslinked Resin

Carbon

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Gel-Type Resin SynthesisGel-Type Resin Synthesis

No internal pore structure in dry stateNo internal pore structure in dry state

Can be reversibly swollenCan be reversibly swollen

Surface Areas generally <10 mSurface Areas generally <10 m22.g.g-1-1

CH CH2

CH CH2

CH CH2

CH2 Cl

CH

CH2

CH2

Cl

+

+

CH CH2

CH CH2

or

80°C

6hr

AIBN (0.75 %wt)

Suspension Polymerisation 212-300m

98 %wt 2 %wt

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g Gel-Type Resin NGel-Type Resin N22

AdsorptionAdsorption

Pseudo-Type II IsothermPseudo-Type II IsothermNon-porous solidsNon-porous solidsInterstitial pores onlyInterstitial pores only

XL01 N2 Isotherm

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

Realtive Pressure (P/P0)

Vo

l Ad

so

rbe

d /

cm

3 .g-1

ST

P

Adsorption

Desorption

BET Surface Area = 1.3805 m2.g-1

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Gel-Type Resin SANSGel-Type Resin SANS

Scattering from interstitial macroporosityScattering from interstitial macroporosity

High error due to incoherent scatteringHigh error due to incoherent scattering

XL01 SANS

0.1

1

10

100

0.001 0.01 0.1

Q / Å-1

dS

/dW

/ c

m-1

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g Hypercrosslinked Resin Hypercrosslinked Resin

SynthesisSynthesis

1,2 Dichloroethane 30 mins

FeCl3 @ 80°C for 3 hrs

Friedel-Crafts reaction

Final structure a function ofFinal structure a function of

SolventSolvent

Swelling TimeSwelling Time

Catalyst AbundanceCatalyst Abundance

Reaction timeReaction time

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HXL Resin NHXL Resin N22 Adsorption Adsorption

Type I isotherm – microporous materialType I isotherm – microporous materialProlonged Hysteresis – broad mesopore Prolonged Hysteresis – broad mesopore distributiondistribution

HXL9 N2 Isotherm

0

200

400

600

800

1000

1200

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

Relative Pressure (P/P0)

Vol

Ads

orbe

d / c

m3.g

-1 S

TP

Adsorption

Desorption

BET Surface Area = 2131 m2.g-1

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HXL Resin SANSHXL Resin SANS

DDff = 2.8 – scattering from volume fractal = 2.8 – scattering from volume fractal

Increase in scattering at high Q - microporosityIncrease in scattering at high Q - microporosity

HXL9 SANS

0.1

1

10

100

0.001 0.01 0.1

Q / Å-1

dS

/dW

/ c

m-1

XL01HXL9Df = 2.8

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Carbon SynthesisCarbon SynthesisC03 Pyrolysis Route

0

200

400

600

800

1000

1200

1400

0.0 50.0 100.0 150.0 200.0 250.0

Time / min

Tem

per

atu

re /

°C

20 K.min-1

20 K.min-1

20 K.min-1

30 min

30 min

45 min Carried out under Argon

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Carbon NCarbon N22 Adsorption Adsorption

Type II isotherm – meso/macroporesType II isotherm – meso/macroporesProlonged Hysteresis – broad distribution of Prolonged Hysteresis – broad distribution of mesoporesmesoporesLow Surface AreaLow Surface Area

C03 N2 Isotherm

0

10

20

30

40

50

60

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

Relative Pressure (P/P0)

Vo

l Ad

so

rbe

d /

cm

3 .g-1

ST

P

Adsorption

Desorption

BET Surface Area = 61.68 m2.g-1

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Carbon SANSCarbon SANS

Increase in whole Q-rangeIncrease in whole Q-range

DDff = 2.6- Weakly Segregated 3D network = 2.6- Weakly Segregated 3D network

C03 SANS

0.01

0.1

1

10

100

1000

10000

0.001 0.01 0.1 1

Q / Å-1

dS

/dW

/ c

m-1

XL01HXL9C03 All Porosity

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Carbon SANS/CM-SANSCarbon SANS/CM-SANS

Large areas of closed porosity over whole Q-rangeLarge areas of closed porosity over whole Q-range

Low mesopores and micropores more abundant in Low mesopores and micropores more abundant in closed porosityclosed porosity

C03 SANS & CM-SANS

0.01

0.1

1

10

100

1000

0.001 0.01 0.1 1

Q / Å-1

dS

/dW

/ c

m-1

Open PorosityClosed Porosity

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ConclusionsConclusions

HXL resins possess a large surface area HXL resins possess a large surface area within a fractal pore structure containing within a fractal pore structure containing large amounts of microporosity with a large amounts of microporosity with a broad distribution of mesoporesbroad distribution of mesopores

Carbons produced from HXL resins, Carbons produced from HXL resins, although having a diminished surface although having a diminished surface area, possess large areas of closed area, possess large areas of closed porosity over the entire rangeporosity over the entire range

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What now?What now?

COCO22 activation and optimisation of carbons activation and optimisation of carbons

Monolithic electrode synthesisMonolithic electrode synthesis

Supercapacitor characterisationSupercapacitor characterisation

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Questions?