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U S
NIVERSITY OF TRATHCLYDE
IN GLASGOW
THE
Che
mic
al a
nd P
roce
ss E
ngin
eerin
g
Hypercrosslinked resins as carbon precursors for supercapacitor
electrodes
Euan Bain
Supervisor: Prof. P. J. Hall
U S
NIVERSITY OF TRATHCLYDE
IN GLASGOW
THE
Che
mic
al a
nd P
roce
ss E
ngin
eerin
g
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
U S
NIVERSITY OF TRATHCLYDE
IN GLASGOW
THE
Che
mic
al a
nd P
roce
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ngin
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g
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
U S
NIVERSITY OF TRATHCLYDE
IN GLASGOW
THE
Che
mic
al a
nd P
roce
ss E
ngin
eerin
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
U S
NIVERSITY OF TRATHCLYDE
IN GLASGOW
THE
Che
mic
al a
nd P
roce
ss E
ngin
eerin
g
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
U S
NIVERSITY OF TRATHCLYDE
IN GLASGOW
THE
Che
mic
al a
nd P
roce
ss E
ngin
eerin
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
U S
NIVERSITY OF TRATHCLYDE
IN GLASGOW
THE
Che
mic
al a
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roce
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ngin
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g
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
U S
NIVERSITY OF TRATHCLYDE
IN GLASGOW
THE
Che
mic
al a
nd P
roce
ss E
ngin
eerin
g
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
U S
NIVERSITY OF TRATHCLYDE
IN GLASGOW
THE
Che
mic
al a
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roce
ss E
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g
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
U S
NIVERSITY OF TRATHCLYDE
IN GLASGOW
THE
Che
mic
al a
nd P
roce
ss E
ngin
eerin
g
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
U S
NIVERSITY OF TRATHCLYDE
IN GLASGOW
THE
Che
mic
al a
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roce
ss E
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eerin
g
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
U S
NIVERSITY OF TRATHCLYDE
IN GLASGOW
THE
Che
mic
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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
U S
NIVERSITY OF TRATHCLYDE
IN GLASGOW
THE
Che
mic
al a
nd P
roce
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g
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
U S
NIVERSITY OF TRATHCLYDE
IN GLASGOW
THE
Che
mic
al a
nd P
roce
ss E
ngin
eerin
g
What now?What now?
COCO22 activation and optimisation of carbons activation and optimisation of carbons
Monolithic electrode synthesisMonolithic electrode synthesis
Supercapacitor characterisationSupercapacitor characterisation
Che
mic
al a
nd P
roce
ss E
ngin
eerin
g
U S
NIVERSITY OF TRATHCLYDE
IN GLASGOW
THE
Che
mic
al a
nd P
roce
ss E
ngin
eerin
g
Questions?