Pitch-based carbon materials COA sent › download › pdf › 36017368.pdf · Petroleum Petroleum...
Transcript of Pitch-based carbon materials COA sent › download › pdf › 36017368.pdf · Petroleum Petroleum...
PitchPitch--Based Based Carbon MaterialsCarbon Materials
Conchi Conchi AniaAnia
InstitutoInstituto NacionalNacional del del CarbCarbóónn, CSIC., CSIC.Oviedo, SpainOviedo, Spain
ITA Annual Conference, Palma de ITA Annual Conference, Palma de MallorcaMallorca, June 2007, June 2007
••IntroductionIntroduction
••Carbon/Carbon compositesCarbon/Carbon composites
••Carbon fibres and synthetic Carbon fibres and synthetic graphitesgraphites
••Materials for energetic applicationsMaterials for energetic applications
••Concluding remarksConcluding remarks
OutlineOutline
Writing(graphite / carbon black)
Writing(graphite / carbon black)
Painting(charcoal)Painting
(charcoal)
Gunpowder(wood based carbons)
Gunpowder(wood based carbons)
Carbon materials. Applications Carbon materials. Applications
Genesis, 6, 14: “Make for yourself an ark of gopher wood; you shall make the ark with rooms, and shall cover it inside and out with pitch”
Genesis, 6, 14: “Make for yourself an ark of gopher wood; you shall make the ark with rooms, and shall cover it inside and out with pitch”
CompositesC/C
Anodes in batteries
Fission /Fussionreactor
Prosthesis andimplants
Carbon materials. Applications Carbon materials. Applications
Aluminum production(anodes)
Electric arc furnace(graphite electrodes) Refractories (ladles)
Aeronautic industry
Saturn V Rocket – Johnson Space Center
Aerospace industry
Competition
HighHigh--tech applicationstech applications
High Temperature Materials!High Temperature Materials!
CARBON MATERIALS
MECHANICAL PROPERTIES•High resistance
ELECTRICAL PROPERTIES•Excellent conductivity
STRUCTURAL PROPERTIES•Graphite-like microstructure
CHEMICAL PROPERTIES•Inertness (except oxygen)
THERMAL PROPERTIES•Superb thermal conductivity
•Low CTE•Temperature tolerance
IntroductionIntroduction
Precursor Intermediate Final product
Gaseous hydrocarbons Carbon black, VGCF, pyrolyticcarbon, fullerenes
Petroleum Petroleum pitchNeedle coke, carbon fibers,
Mesophase pitchMesophase microspheres, carbon fibers, foams
Coal
Charcoal Activated carbons
Coal- tar pitch CTP
Polymers andprepolymers
PAN
ResinsPolyimides
Biomass
Carbon fibers
Vitreous (glassy) carbon
Monoliths, graphite films
Coal
Carbon precursors and materialsCarbon precursors and materials
Needle coke, carbon fibers
Hydrocarbon Graphite
Synthetic diamond Pyrolytic carbon
Nanotubes
VGCF Carbon black
Cat. H2 + CH4
H
Air
Cat. + CH4
T
Carbonfilms
Electricdischarge
He
Ions
SWNT
Laser
Carbon precursors and materials: gas phaseCarbon precursors and materials: gas phaseCarbon: 1s2, 2s2, 2p2
Flexible coordination chemistry (sp, sp2, sp3), allowing infinite 3D architectures
Organicprecursor
Graphitizable
(Anisotropic)
Non graphitizable
(Isotropic)
Mesophase
Fibers
Cokes
Foams
Fibers
ActivatedcarbonsVitreous
carbons
graphites
Diamonds
Pitch
Polymers
Biomass
Coal
Carbon precursors and materials: liquidCarbon precursors and materials: liquid--solid phasesolid phase
Carbon precursorsCarbon precursors
Mesophase
Carbonmaterial
50 μm
Pitch Mesophase pitch
Pitch: A carbon rich source
••IntroductionIntroduction
••Carbon/Carbon compositesCarbon/Carbon composites
••Carbon fibres and synthetic Carbon fibres and synthetic graphitesgraphites
••Materials for energetic applicationsMaterials for energetic applications
••Concluding remarksConcluding remarks
OutlineOutline
C/C compositesC/C composites
C/C Composites AdvantagesHigh temperature materials
Thermally stable solidsHigh resistance to thermal shock due to their thermal conductivity and low thermal expansionRetain and even improve their mechanical properties at high temperature
Chemical inertnessLow weightOptimum fatigue resistanceCorrosion resistanceBiocompatibility
C/C Composites AdvantagesHigh temperature materials
Thermally stable solidsHigh resistance to thermal shock due to their thermal conductivity and low thermal expansionRetain and even improve their mechanical properties at high temperature
Chemical inertnessLow weightOptimum fatigue resistanceCorrosion resistanceBiocompatibility
C/C DisadvantagesSensitive to high temperature oxidationPrice
C/C DisadvantagesSensitive to high temperature oxidationPrice
Temperature (°C)
0 200 400 600 800 1000 1200 1400 1600 18000
10
20
30
40
UTS
/Den
sity
x 10
6(m
m)
Titanium 35 % - Fibres SiC (0°)
35 % B4C (particles) - Ti
Titanium
Ni
SiC - SiC
Columbium (Nb) C129Y
Carbon - Carbon
Carbon - CSi
35 % B4C (particles) - Ni
High temperature materialsHigh temperature materials
Carbon Carbon fibresfibres. Variety of architectures. Variety of architectures
Preform
3-D2-D
2-D 1-D
Matrix precursorsMatrix precursors
ResinsThermosetting
Thermoplastic
Pitches
Coal-tar pitch
Petroleum pitch
Synthetic pitch
Matrix precursor
Pitch vs. Resin Advantages
Higher carbon yield
Graphitizability
Development of open porosity on carbonization
Wide variety of structures and properties
Price
Pitch vs. Resin Advantages
Higher carbon yield
Graphitizability
Development of open porosity on carbonization
Wide variety of structures and properties
Price
Low volume variation on carbonization
Material damage
Low volume variation on carbonization
Material damage
Affinity to the fibre surface
Fibre/matrix adhesion
Affinity to the fibre surface
Fibre/matrix adhesion
Adequate viscosity
Effective impregnation
Adequate viscosity
Effective impregnation
High carbon yield
Process efficiency
High carbon yield
Process efficiency
Composite preparationComposite preparation
CARBONFIBRE
CARBONFIBRE
MATRIXPRECURSOR
MATRIXPRECURSOR
IMPREGNATIONIMPREGNATION
CARBONIZATIONCARBONIZATION
DENSIFICATIONDENSIFICATION
GRAPHITIZATIONGRAPHITIZATION
IMPREGNATIONIMPREGNATION
CARBONIZATIONCARBONIZATION
PITCHPITCH
C/C COMPOSITEC/C COMPOSITE
ΔP
2D-PREPREG
1D-PREPREG
HEAT SOURCE
PULLING DEVICE
HEAT SOURCE
PULLING DEVICE
HEAT SOURCE
PULLING DEVICE
1D-PREPREG
nD-PREPREG
Pressure
Vacuum
Wet-windingWet-winding
PultrusionPultrusion
InjectionInjection
Hot-press mouldingHot-press moulding
Composites. The effect of the precursorComposites. The effect of the precursor
CC-B-CTP CC-I-CTP
CC-LP CC-PP
14 μm
BINDER CTP (BP)
PETROLEUM PITCH (PP)
LIQUEFACTION PITCH (LP)
IMPREGNATION CTP (IP)
Composites. Pitch densificationComposites. Pitch densification
n-cycles
PITCH LIQUIDIMPREGNATIONPITCH LIQUID
IMPREGNATION
UNDENSIFIEDC/C COMPOSITEUNDENSIFIED
C/C COMPOSITE
DENSIFIED C/CCOMPOSITE
DENSIFIED C/CCOMPOSITE
CARBONIZATIONCARBONIZATION
Impregnating CTP
Modification of the matrix precursor. Pitch thermal treatmentModification of the matrix precursor. Pitch thermal treatment
Impregnating CTP
Slight increase in granular microstructuresDecrease in porosityVirtual elimination of microcracksImprovement in mechanical properties
CC-ORIGINAL
Density= 1,50 g cm-3
Porosity= 16 vol %ILSS= 15 MPaFS= 416 MPa
Density= 1,50 g cm-3
Porosity= 16 vol %ILSS= 15 MPaFS= 416 MPa
CC-400 °C /5 h CC-400 °C /7 h
10 μmDensity= 1,60 g cm-3
Porosity= 12 vol %ILSS= 39 MPaFS= 487 MPa
Density= 1,60 g cm-3
Porosity= 12 vol %ILSS= 39 MPaFS= 487 MPa
Density= 1,65 g cm-3
Porosity= 9 vol %ILSS= 44 MPaFS= 575 MPa
Density= 1,65 g cm-3
Porosity= 9 vol %ILSS= 44 MPaFS= 575 MPa
Modification of the matrix precursor. Pitch oxidative treatmentModification of the matrix precursor. Pitch oxidative treatment
CC-300 °C/AIR
CC-I-CTP
FS = 416 MPaFS = 416 MPa
CC-250 °C/AIRCC-250 °C/AIR
FS = 644 MPaFS = 644 MPa
CC-275 °C/AIRCC-275 °C/AIR
FS = 609 MPaFS = 609 MPa
10 µm
FS = 432 MPaFS = 432 MPa
Impr
egna
ting
CTP
Granular compositesGranular composites
00,10,20,30,40,50,60,70,80,9
1
0 500 1000 1500 2000 2500 3000 3500 4000Tiempo (s)
Coe
ficie
nte
de fr
icci
ón
GR AT ATGR Freno-B
Pitch-based conventional brakes
Fric
tion
coef
ficie
nt
Time (s) Brake B
Pitch infiltration in carbon Pitch infiltration in carbon preformspreforms
PREFORMPREFORMMatrix precursor•Fluid•High carbon yield
Matrix precursor•Fluid•High carbon yield
Problems•Homogeneity•Bloating on carbonization
Problems•Homogeneity•Bloating on carbonization
Anthracene oil-basedpitches (mesophase)Anthracene oil-basedpitches (mesophase)
••IntroductionIntroduction
••Carbon/Carbon compositesCarbon/Carbon composites
••Carbon fibres and synthetic Carbon fibres and synthetic graphitesgraphites
••Materials for energetic applicationsMaterials for energetic applications
••Concluding remarksConcluding remarks
OutlineOutline
Carbon Carbon FibresFibres from pitchesfrom pitches
SpinningSpinning
Green fiber(isotropic)
Green fiber(isotropic)
Stabilized fiber(isotropic)
Stabilized fiber(isotropic)
Carbonized fiber(anisotropic)
Carbonized fiber(anisotropic)
StabilizationStabilization
CarbonizationCarbonization
GrafitizationGrafitization
General Purposes CarbonFiber (GPCF)
General Purposes CarbonFiber (GPCF)
High Performance CarbonFiber (HPCF)
High Performance CarbonFiber (HPCF)
Green fiber(anisotropicGreen fiber(anisotropic
Stabilized fiber(anisotropic)
Stabilized fiber(anisotropic)
Isotropic fiberprecursor
Isotropic fiberprecursor
Anisotropic fiberprecursor
Anisotropic fiberprecursor
Carbon Carbon FibresFibres from pitches from pitches -- IIII
TREATED CTP
ISOTROPIC PHASEMESOPHASE
ISOTROPIC FIBRE
CTP (Impregnating)CTP (Impregnating)
Thermal TreatmentThermal Treatment
FiltrationFiltration
Free-QI-Pitch(PP, AOP)
Free-QI-Pitch(PP, AOP)
Thermal TreatmentThermal Treatment
SedimentationSedimentation
TREATED PITCH
MESOPHASE
GRAPHITIC FIBRE
Limitation factor:QI particles
Isotropic carbon Isotropic carbon fibresfibres
200 μm 10 kVINCAR-CSIC
20 μm 10 kVINCAR-CSIC
Ø = 35 μmTS = 143 MPaE = 28.9 GPa
Ø = 16 μmTS = 414 MPaE = 36.6 GPa
Graphitic carbon Graphitic carbon fibresfibres
Partially graphitic carbon fibers
Graphitic carbon fibers
Synthetic Synthetic polygranularpolygranular graphitesgraphites
TREATED CTP
MESOPHASEISOTROPIC PHASE
CTP (Impregnating)CTP (Impregnating)
Thermal TreatmentThermal Treatment
FiltrationFiltration
Free-QI-Pitch(PP, AOP)
Free-QI-Pitch(PP, AOP)
Thermal TreatmentThermal Treatment
SedimentationSedimentation
TREATED PITCH
GRAPHITE
MESOPHASE
Self-sintering
Mesophase plasticity(stabilization)
Synthetic Synthetic polygranularpolygranular graphitesgraphites -- IIII
FS ~ 100 MPa ρ ~ 10 µΩ m dH2O ~ 2 g cm-3FS ~ 100 MPa ρ ~ 10 µΩ m dH2O ~ 2 g cm-3
••IntroductionIntroduction
••Carbon/Carbon compositesCarbon/Carbon composites
••Carbon fibres and synthetic Carbon fibres and synthetic graphitesgraphites
••Materials for energetic applicationsMaterials for energetic applications
••Concluding remarksConcluding remarks
OutlineOutline
235U + 1n → 236U → F1 + F2 +1n + energy
Graphite is one of the structural components of the reactors. It acts as “moderator”, protecting the fuel and maintaining fission reaction by converting fast neutrons into low energy ones, that can be absorbed for activating the 235U isotope
Nuclear Fission ReactorsNuclear Fission Reactors
As structural material in the HTGR core, graphite has excellent properties such as low neutron absorption, minimal radiation damage, superb heat resistance and high thermal conductivity.
Materials of high thermal conductivity, low porosity, high mechanical strength and low erosion by hydrogen impact
First reactor wallH + H → He
‘Endless’ source of energy
Nuclear Fusion ReactorsNuclear Fusion Reactors
FP6 Priority 3 FP6 Priority 3 Nanotechnology and nanosciences, knowledge-based multifunctional
materials, new production processes and devices- ‘NMP’
Integrated Project:
New Materials for Extreme Environments (EXTREMAT)
Integrated Project:
New Materials for Extreme Environments (EXTREMAT)
Consortium of 38 institutions from 13 countries
C/CC/C Doped C/CDoped C/C
Ti, V, Zr, WTi, V, Zr, W
Methods for introducing dopants
Mixture of mesophase pitch with:
• Ti(OBu)4• TiC nanoparticles (130 nm)
Decomposition of Ti(OBu)4 on CF:
• Using an oxidant (H2O2)• Thermal decomposition
Mesophase pitch
densificationDopant
Fibre preform
Doped CFC
Fibre preform
Doped CFC
densification
Dopant
112
2
5 µm20 µm
EXTREMAT EXTREMAT
Portableelectronic devices
Electricvehicles
Energy STORAGE Energy STORAGE
Alternative energysources
Energy productionoutside CO2 cycle
H2 + O2 → H2O
SupercapacitorsFuel Cells
Energy storage and production
LixC6
A
Li(1-x)MO2
e-
e-
e-
e-Li+
Li+
Li+
Li+
-- ++e- e-
Electrolyte
e-
e-
e-
e-
Li-ion battery
Comparison power/specifc energy of different devices
10
103
104
105
106
107
102
0.05 0.1 0.5 1 5 10 50 100 500 1000Specific energy (Wh/kg)
Spec
ific
powe
r(W
/kg)
Batteries Fuel cells
Capacitors
Electrochemicalcapacitors(supercapacitors)
Batteries:Higher storage of energyCheaperMore developed
Supercapacitors:Higher powerFree of mantainanceMore environmentally friendly
Supercapacitors can increase the life of a battery if they are coupled together. Supercapacitor will supply the power peaks. This will enable a significant reduction ofbatteries size.
Energy storage Energy storage
> 1000 1 - 103150 50-250Batteries
<1 105 - 106102 - 1030.5 - 15 Supercapacitors
Discharge time (s)Cyclelife
Power density (W/kg)
Energy density (Wh/kg)Device
Anode: graphitic carbon material
C + x Li+ + x e- LixC
Cathode: transition metal oxide (LiMO2)
LiMO2 Li1-xMO2 + x Li+ + x e-
M= Mn, Co, Ni
Electrolyte: LiPF6 in PC
In 1991, Sony developed the first commercial Li-ion battery
The capacity to insert Li+ depends on the crystalline structure
Low temperature carbons: higher irreversibility. Pre-treatments required
Graphite (theoretical capacity 372 mAhg-1)
Zone 1
Zone1
500 1000 1500 2000 2500 30000
200
400
600
800
1000
S pec
ific
capa
cit a
n ce
(mAh
g-1 )
Thermal treatment (ºC)
…. Graphitisable
…. Non Grafitizable
Zone2
Zone3
Energy storage: lithium ion batteries Energy storage: lithium ion batteries
⇔
⇔
0
100
200
300
400
500
600
700
800
900
0 5 10 15 20Nº cycle
Cap
acity
(mA
h/g)
VR17(750-6)cC50VR14(750-6)cC50VR15(750-6)cC50VR12(750-6)cC50VR16(750-6)cC50
SnO2V2O5NiO
OriginalFe2O3
The addition of a dopant (Sn, Ni, Fe) improves the behaviour of the carbon materials by increasing the cyclability.
Graphite (theoretical capacity 372 mAhg-1)
Energy storage: lithium ion batteries Energy storage: lithium ion batteries
Energy storage: supercapacitorsEnergy storage: supercapacitors
Energy stored = ½ (CV2)
Voltage = f (electrolyte)
Capacity = f (electrode material)
C ~ C double layer + C pseudo-capacitance
Double Layer Capacitance: Non-Faradaic process
dSC ε= Csp = 10-50 µF/cm2
d double layer~ 1nm
Example:
SBET = 1000m2/g Cmax≈ 200 F/g
Fast Faradaic redox process
Ox + ne- ↔ RedC = dq/dV
..][wm
FnRedq ⋅⋅=
Csp(theoretical)=100-400µF/cm2
Example:
SBET=250m2/g Cmax≈ 500-1000 F/g
Activated carbon - High surface area- Suitable pore size (depending on
the electrolyte)- Suitable surface chemistry- High electrical conductivity
Energy storage: supercapacitorsEnergy storage: supercapacitors
Pitch-based carbon
6 KOH + 2C→2K + 3H2 + 2K2CO3
Cell assembling
Electrodes
Separator
Currentcollector+ -
Chemical activation
Etching + Washing
Pitch + Stabilization
vs
Adequate pore size distribution
Suitable surface chemistry
Energy storage: supercapacitorsEnergy storage: supercapacitors
Pitch-based carbon
O
O
+ 2 H + 2 e + -
OH
OH
OO
OO+.
+ 1 e-
+OO-
O
O
OH O OH
O.
+
+ 1 e -+O OH
O-
-500
-400
-300
-200
-100
0
100
200
300
400
500
-0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6
E, V vs. Hg/Hg2SO4
C, F
/g
C=101 F/gC= 214 F/g
0
100
200
300
400
500
0 20 40 60 80
Current density (mA/cm2)
Sp
ecif
ic c
apac
itan
ce (
F/g
SP4-1
SP4-2
SP4-3
SP4-5
Activated carbons obtained by chemical activation of mesophase pitch yield extremely high values of capacitance (~400 F/g compared to 150-200 F/g of best conventional activated carbons and ~50 F/g of carbon nanotubes).
Energy storage: supercapacitorsEnergy storage: supercapacitors
CYCLEABILITY
A high electrochemical stability is found up to 10000 cycles indicating that the pseudocapacitance effect introduced by oxygen functionalities is stable with cycling
Galvanostatic charge/dischargeMaximum cell voltage: 0.6 VCurrent density: 100 mA/g
0
50
100
150
200
250
300
350
400
0 2000 4000 6000 8000 10000
Cycles
Capa
cita
nce
[F/g
]
0%
20%
40%
60%
80%
100%
120%
Energy storage: supercapacitorsEnergy storage: supercapacitors
GAlvanostatic Charge /discharge (200 mA/g)Voltage : 1.2 V
0
50
100
150
200
250
300
350
400
0 2000 4000 6000 8000 10000
Cycles
Capa
cité
(F/
g)
1.2V
0.6 V
0.00
0.20
0.40
0.60
0.80
1.00
1.20
0 2000 4000 6000 8000 10000
Cycles
C /
Co
1.2 V
0.6 V
YY--ANAN-- 4 4 WhWh/kg /kg atat 0.6 V 0.6 V
15 15 WhWh/kg /kg atat 1.2 V1.2 V
NoritNorit-- 2 2 WhWh/Kg /Kg atat 0.6 V0.6 VStoredStored energyenergy::
H2SO4 1M
CYCLEABILITY Energy storage: supercapacitorsEnergy storage: supercapacitors
CA
RB
ON
MA
TER
IALS
Chemistry
Biotechnology
Friction/lubricants
Implants
Energy
Constructi
on
Industry Al
•Hydrogen storage•Adsorbents•Molecular sieves•Catalyst support
•Immobilizaton of biomolecules•Enzyme support•Carriers in drug delivery
•Sportive material•Civil constructions•Aeronautic•Thermal insulators
COAL-TAR PITCH
Concluding remarksConcluding remarks
Multidisciplinar Research
Concluding remarksConcluding remarks
Thank you for your attention!!!