November 21st , 2012
LectureFunctional Carbon Materials forEnergy and Environmental Devices
Yoon, Seong-Ho, Jin Miyawaki
IMCE, Kyushu University
6-1 Kasuga-Koen, Kasuga, Fukuoka, Japan 〒 816-8580
yoon@cm.kyushu-u.ac.jp

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Application of carbon materials
Electric and Heat Conductions
 Conductor and Semi-conductor

Energy Storage Battery anode Super capacitor
 Gas storage

MechanicalReinforcement

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Environmental Protection
 Activated surface

High Temperature
Materials

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Applications of Carbons
FED

ITO
alternative

Nano-robot
Bio-chipDisplay

MemorySolar cell
Field emission

Wastewater
treatment
Organic
reactionNanoreactor

DDS

BioIT

Fibril,biocompatibility

AFM/STM

Nano-Eng.

Environmental

Nano-lithography

Nano-fibril

FET・TMR

Catalyst
SupportElectron spintransportation

Electric Devices

Nano-poreGasstorage

Dielectric

EnergyIon
storage

EMS

Electricsalination

CVD/synthesis

Package
Antistatic

Etc.
Arc/Laser ablation

IMCE, Kyushu University3Characteristics of carbons● Thermal stability● High thermal and electric conductivities
SWNT, Diamond : 4000 W/mK, K-11
carbon fiber: 1100 W/mK
● Small heat expansion● High thermal shock properties● High chemical stability● Abrasion and lubricant properties● High mechanical properties
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4Thermal characteristics of carbons

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5BondingHybridization

Allotropes

SP3

Cubic diamond

Derived and Defective Forms

Diamond-like Carbon

Polycrystalline
Graphite

Pyrocarbons

Carbon Black

SP2

Cokes andActivatedCarbons
Carbon Fibers

Hexagonal graphite

Bucky Onions

Toroidal Structures

Acetylene Blacks

SP2+

rehybridization

Nanotubes

FullereneRef.) Bourrat, X. Structure in Carbons andCarbon Artifacts. In: Sciences of Carbon
Materials. Marsh, H.; Rodriguez-Reinoso, F.,
Eds., Universidad de Alicante, 2000. pp1-97.

SP1Carbyne

Carbon Allotropes
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Molecular structures of graphite

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Conventional Fossil Fuels

Petroleum

Exploration and Production, Refiningof Heavy Fraction to Very Clean Fuel

Coal

Clean Coal Technologies
Efficient Combustion
Gasification
Liquefaction

Natural Gas Transportation
LNG or Pipe Line
GTL: Small Resources
Price and Cost :IMCE, Kyushu University

Ultimate Recoverable Quantity14化石燃料の将来

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炭素材料原料
Raw materials
Coal tarPolymer: Thermosetting and thermoplastic
Heavy oil and residues
BiomassPrecursor• Pitches: CF, ACF, MCMB, Ball type AC, Binder pitch,Additives• Polymer: AC, ACF, Glassy carbon, CF• Cokes: Electrode, Capacitor, Battery anode, AC,Additives• Char: AC, Additives, Reducer for Solar cell
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From fossil fuel to functional carbons
Carbonaceousresources

Side products

Advanced Carbon Materials for Energy Saving, Storing,
And Environmental Protections and Improvements

Effective conversion and utilization of fossil fuels and their residues
Petroleum

Heavyresidues

Natural Gas

C10+Syngas

Coal

Coke

COG

Energy Saving

Energy Storing

EnvironmentalProtections

Fuel Cell

Battery

Water

Catalyst

Li-ion battery

Purification

Separator

Na-S battery

Water conversion

Bipolar Plate

Air battery

NO3-, PO4-3 removalSuper capacitor

Atmosphere

EDLC for EV, FV

AC, ACF for DeSOx,
DeNOx, deVOCs

Hydrogen

AC, ACF for
Sick-house gases

Advanced
Generation
Structural Materials
For IGCC, IGFC

Structural Materials
H-storing Bombe
For Atomic Reactor

Tar

Biomass

CharLight Weight

MethaneCarbon Fibers

Methane storage

CO2 separation &Concentration

Synthetic Carbon

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17ピッチ系高性能炭素繊維
メゾフェーズ
ピッチ

紡糸

不融化

炭化・黒鉛化

高弾性、高引張強度、高熱・電気伝導度

問題点：低圧縮強度 > 複合材料使用制限

原因：ドメイン（プリット構造）の大きさ・均一さ

Pleat構造 ＞ 均一・縮小 ＞ 圧縮強度向上IMCE, Kyushu University

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Classification of Carbon Fiber
8.0
T1000G

7.0

・ Ultra High Modulus Type（ＵＨＭ）
Young’s Modulus > 600ＧＰａ
Tensile Strength > 2500ＭＰａ

Tensile strength (GPa)

6.0

5.0
T700S
T300J

4.03.0

T800HIM
T400H

HT・ High Modulus Type（ＨＭ）
Young’s Modulus ：350～600ＧＰａ
Tensile Strength > 2500ＭＰａ

M35J
M40J
M46J
M50J

M30

Granoc YS series
M60J

HM

UHM

Granoc XN seriesT300
M46

LU・ Standard Modulus Type（HT）
Young’s Modulus ：200～280ＧＰａ
Tensile Strength > 2500ＭＰａ

Kureha CFs・ Low Modulus Type（ＬＭ）
Young’s Modulus < 200ＧＰａ
Tensile Strength < 3500ＭＰａ

M40

M50

2.0

・ Medium Modulus Type（ＩＭ）
Young’s Modulus ：280～350ＧＰａ
Tensile Strength > 3500ＭＰａ

1.000100

200300

400

500

600

700

800

900 1000

Young’s Modulus (GPa)

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20CFs for Construction

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21WindmillWind power generation which has
become popular recently isexpected to require bigger andbigger blades to have higher andhigher output capacity for each unit.
In order to support big size blades,
use of CFRP becomes vitallynecessary. And as the materialfor high speed rotating body for
fly wheels which are attracting
public attention as a technology
to store energy effectively basedon theory of top spinning, use ofCFRP is becoming popular.

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Research background : Battery Road

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Small fuel cells

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Semi-conductors

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Characterization of ACF purificationNONO

Natural ventilation

NO2NO2ACF(SPM)
Hazardous
chemicals
Odor
NH3SO2Room temperature, ozonizer is no need,no light irradiation, compact design
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IMCE, Kyushu University43炭素材の製造

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Phase of reaction
Heat treatment
Temperature
(oC)

Vapor

SolidLiquid

Organic materials

Structural units
Molecular

Structures

Cluster

RadicalPyrolysis

Aromatization
PolyconCrosslinking
densation

500
Carbon materials

600

Carbonaceous
materials

Coking

DomainPore

From
Fromsolid and liquid
vapor phases phases

Microdomains
rawmaterials

Organic materials

200탄소화

Microdomain

Applications

PartialmergerNucleation of Microof cluster
domainsLa
increasing

PyroCarbons
Nucleation(Coatingof domain Nucleation C/C etc)
by merger of microof micro- poresdomains
Fibrouscarbons

1000
탄화

CarbonMaterials
1500

Decreasing
microspores

Shrinkage ormetamorphosisof microdomains Shrinkage ormetamorphosis
Lcof domains
increasing

Activatedcarbons
GlassyNeedleor hardcokecarbons Carbon
fiber
(HT)

DLC

2000
흑연화

Graphites

Glassy Carbon
carbons fiber(HM)

Lc(112)increasing

3000

ElectrodeLi
battery C/C

HOPG

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Heat treatment
Temperature (oC)

Phase of reaction

Vapor

Solid

LiquidGas
volatilization

Chemical andPhysical changes

Organic materials
200
탄
소화

RadicalPyrolysis

Aromatization
PolyconCrosslinking
densation

500
Carbon materials

600

Carbonaceousmaterials

Coking1000
탄화CarbonMaterials
1500

2000
흑
연
화

Graphites

Molecular
Structures
Organic materials

H2O
Main chain rearrangements
Low mol. Paraffin or Olefins
Aromatization, Condensation
Low mol. Aromatic carbons
Polymerization, Cross-linking
CokingCH4, CO, NO2
H2S, CO2
H2 etc.

Devolatilization
Crack nucleation
Stacking startLoss of viscosity (Inorganic Mat.)

H2CO, CO2
H2Setc.

Removal of heterogeneous atoms
Dehydrogenation
Micropore nucleation
La increasing

H2SHCN
CS2N2 etc.
H2H2S
N2 etc.

Removal of heterogeneous atoms
Lc increasing
Reducing micro pores

Removal of inorganic materials
Formation of 3 D graphitic structure

3000

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化石燃料から高機能性炭素材の製造と応用

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人造カーボンの構造の由来

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PAN系炭素繊維の構造

IMCE, Kyushu University49単位構造と構造の制御
fiber axis
Aromatic planar moleculespinningLc(002)
Deformed micro-domain
Stacking unit of planar molecules(Molecular assemble unit)

Closely packed microdomains in mesophasepitchAligned micro-domains inthe mesophase pitch fiber

Graphitic unit
Micro-domain(Quasi-aligned molecular assemble unit)

DomainHeat
Treatment

Pitch fiber

Pleat unit

Graphitized fiber

IAMS, Kyushu University “Axial nano-scale microstructure in the graphitized fiber inherited from liquid crystal mesophase pitch”
IMCE, Kyushu University Carbon, 34, 83-88 (1996) S. H. Yoon, Y. Korai, K.Yokogawa, S. Fukuyama, M. Yoshimura, I. Mochida 50

構造概念からの炭素材IMCE, Kyushu University51

構造の制御はどこから?

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Purities of Advanced Materials• High performance pitch based carbon fibers:less than 50 ppm• Capacitor : less than 500 ppm• High performance needle coke : 500 ppm• Carbon medicines: less than 300 ppm?
• Carbon anode for LIB: less than 100 ppm• …

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Mechanical Properties of Carbon Fibers○ PAN-CF△ Rayon-CF□ Pitch-CF

Tensile Strength（kgf/mm2)

800
700
600
500

AR Mesophase Pitch
Based HPCF

400
300
200

Conventional PitchBased HPCF

10000

102030405060

708090Young’s Modulus（ton f/mm2)

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Nano-carbons
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Fullerene

Zero dimension
Basal surface
Nano-size

High price, very limited application
Mass-production (Solved)(Frontier Carbon)

CNT

One dimension
Basal surface
Nano-size

Relatively high price (Under study)
Patent problems (?)
Mass-production
Limited application

Various surfaces
and structures
Nano-size

Relatively low price
Patent problems (Solved)
Mass-production (Solved)
Various applications
Large diameter (Solved)

Dimension-lessParticular surfaces

Relatively low price
Patent problems (Solved)
Mass-production (Solved)
Various applications

CNF

Graphene

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58Selective Preparation of CNFs and Relatives
Standard CNFs
PCNF, HCNF, TCNF
Accordion CNF

Target optimized CNFs

Mass Production of CNF
Batch process
Pressurized Process
CNFs from Waste Gases

Small CNF,
High SA CNF,
Highly Graphitic CNF
Highly Dispersive CNF
N-doped CNF

Structural Modifications
Mesoporous CNFs

Activation

CNF functional composites
CNF-Si, SiO, TiSi
CNF-NG、CB
CNF-SiO2, CNF-MgOMetal & Metal Oxide Nano-chain

Electric oxidation

Electro-spun CNF
Indoor pollutions
Dilute NOx
De-metal, De-particulates¥

Fe3O4, MoO2 nanochain
SiO2, SiC nanofibers
Pt, PtRu, Pd, Au nanochain

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65What is a functional Nano-material
Functional
Material
Adsorption
Support

Improvement of
Functions byGrowing CNFs

Function improvement
Function Hybridization
Novel Function Creation

ElectrodeFilleretc.
Pretreatment ofSurfaceCatalyst supporting

CNF Growth

Functional
Material

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Various CNF Composites

IMCE, Kyushu University“Surface Control of Activated Carbon Fiber by Growth of Carbon Nanofiber”
Seongyop Lim, Seong-Ho Yoon, Yoshiki Shimizu, Hangi Jung, and Isao MochidaLangmuir; 2004; 20(13) pp 5559 – 5563

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68Research scope of Yoon’s Lab

 Synthesis and applications of functional materials
 Energy and environmental engineering- Outline and Interrelation of Research Topics
Advanced Catalytic Reaction

Environmental Preservation

Coal and Petroleum - Selective ReactionsHydrogenation・C1, C4 Chemistry、Highly-purified Fuel

Adsorptive Reaction：DeSOｘ、DeNOｘ
Selective Ads.：VOC、CO2、Black carbon,
Sick house gas, Nano-particles
Gas storage and separation：CH4, H2

Catalyst Preparation

Metal, Oxide, Complex, Oxygen, Microorganism

Liquefaction・gasification
refining and reforming

Calcination
Graphitization

Refined Precursors
Gas Oils

Meso-fication
Carbonization

Coal and Petroleum
Oil Shell
Tar

Functional Carbons

Functional Composites

Activated Carbons and Fibers (AC, ACF)
Carbon Fibers (CF)Needle Cokes
Green Cokes and Calcined Cokes
Binder Pitch
Mesophase Pitch
Carbon Nanofibers （CNF)
Fullerene and its Derivatives

Hydrocarbons
Organic Materials
Biomass

Composite
ArtifactCarbonization
CVDMixing

CF-Composites
AC, ACF Adsorption
Electrode
Cokes, Binders
CNF-Composites
Nano-particle Composites
Inorganic Nanofibers

Chemical, Electrochemical Modification
Composite and Functionalizing

Fundamentals of Carbon Engineering

EnergyAdvanced Materials

Carbon Structure Fundamentals：modeling and functional prediction ofstructural units of CF, ACF, and CNF
Control and Uses of Surface and Pore Structure
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Thermaland Kyushu
Electrochemical
Characterization of Carbons

High Functional Li-ion secondary battery
Supercapacitor Materials
Desalination：fresh water making
Fuel Cell Catalysts, Separators

Field Emission Display
Transparent Conductive Films
EMI Shield、Sensors
ER Fluid, Nano-fluid69

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Carbons from now
Era of nano-carbons are almost finished. Only special applications are promising!
Era of GOOD Raw material to GOOD Product are almost finished. China and otherdeveloping countries will take over whole markets!

Era of BAD Raw material to GOOD Product are coming. Developed countries only havechances on such materials
Novel carbon, if it can be found, still has a chance to change the paradigm.
But what is that?

Nano-carbons(Concept, methodology)

FusionConventional carbons(Waste Materials)

New carbon materials, New processes for manufacturing, New markets for carbon
applications
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New Carbonaceous Materials Technology
New feasible technology to solve urgent energy and environmental
problems which fusion conventional fuel science, carbon technology
and nano-carbon technology.
Fossil Fuel Science & Technology• Petroleum Chemistry, Technology• Coal & Biomass Sciences• Catalyst, MiningConventional Carbon Technology• Carbonaceous Materials Sciences• Carbon Technology• Carbon alloy science• Activated carbon science

Nano Carbon Technology• Nano structural concept• Nano technologic method

Why New Carbon Technology through the fusionof Conventional and Nano Carbon Technologies ?
 Innovation of performances of carbon materials.
 Consumption of fossil fuels grows by 2~3 times up to 2050.
- High utilizations of fossil fuels and biproducts,
73- Decreasing environmental burdens
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Conclusion• Carbon is Key Materials for Energy andEnvironmental Devices.
• High Utilization of Fossil Fuels and Their Biproducts is most urgent task to solve.
• New Structural Concept and Producing Method
Can Increase the Industry Realization.
• Best Structure Must Be Selected For Each
Objective and Prepared.
 Preparation step (Selective and Controlled Synthesis)
 Modifications⇒• It is time to re-innovate!
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Report1. 炭素材が省エネルギー・環境保全デバイスのKeyマテリア
ルになる理由を分子構造、物性の側面から記述せよ。
（半ページ程度）
2. 比表面積を増やすにはどうすればよいか？
炭素材に細孔を導入する手法としてガス賦活（物理賦活）と薬品賦活（化学賦活）がある。それぞれを説明せよ。
• 提出期限：次の授業時間まで• Word Processorを使わずに作成すること。
• A4 1枚で作成すること。
• 授業日時と講義者（Yoon教授）を明記すること。
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