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






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


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


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



CC-400 °C /5 h CC-400 °C /7 h

10 μmDensity= 1,60 g cm-3








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


CC-275 °C/AIRCC-275 °C/AIR


10 µm


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)






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)



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)


FiltrationFiltration




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






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


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


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).


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%


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!!!

Pitch-based carbon materials COA sent › download › pdf › 36017368.pdf · Petroleum Petroleum...

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