2011/10/28

Characteristic Performances of Carbons

素子材料基礎第2講義
Oct. 26, 2011

Electric and Heat Conductions
 Conductor and Semi-conductor

第4章 炭素物質の電子状態と化学反応性

Energy Storage Battery anode Super capacitor
 Gas storage

尹 聖昊
九州大学先導物質化学研究所

Environmental Protection
 Activated surface

MechanicalHigh Temperature
Reinforcement Materials

1

Applications of Carbons
FED

ITO
alternative

Nano-robot
Bio-chipDisplay

MemoryIT
Field emission

Organic
reactionNanoreactorDDS

BioSolar cell
Wastewater
treatment

Characteristics of carbons

Fibril,biocompatibility

AFM/STM

Nano-Eng.

Environmental

Nano-lithography

Nano-fibril

FET・TMR

Catalyst
SupportElectron spintransportation

Electric Devices

Nano-poreGasstorage
Ionstorage

EMS
DielectricEnergy
Electricsalination

CVD/synthesis

Package
Antistatic

Etc.
Arc/Laser ablation

 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 properties1

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BondingHybridization

Allotropes

SP3

Cubic diamond

Derived and Defective Forms

Thermal characteristics of carbons
Diamond-like Carbon

Polycrystalline
Graphite

Pyrocarbons

Carbon Black

SP2

Carbon Fibers

Hexagonal graphite

Bucky Onions

SP2+εrehybridization

Cokes andActivatedCarbons

Toroidal Structures

Acetylene Blacks
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.

SP1
CarbyneCarbon Allotropes2

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Molecular structures of graphite3

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NANOPHASED CARBON MATERIALS
ArmchairSingle-walled

CNT(Carbon nanotube)

ChiralMulti-walled
Zig-zag
Platelet

CNF(Carbon nanofiber)

Herringbone
Ribbon

CNP(Carbonnanoparticulate)

CNH(Carbonnanohorn)

Fullurenes, Pyrocarbons
And Carbon blacks

What is the synthetic carbon!
Origin of Structural Units And Crystalline Defects
Organic materials
Basic structural units
2 ~ 10 nm

Heat treatment

CarbonMicro domain 4 ~ 6 nm

Orientation
Rearrangement

Coagulation
Partial melt fusion

DomainGas
LiquidSolid

Modified Structures

Carbon or carbonaceous materials
Varieties of structural unit
Heat treatment

Multi-walled
CNC(Carbonnanocell)

Fullerenes

Fullerenes

Pyrocarbons
Carbon blacks

Gaint fullerenes

How to make synthetic carbons
Selection of Precursor

Carbonization

FormingStabilization

Gasphase catalytic
Non-catalytic

Calcination

Graphitization

Activation-Heat treatment

Nano-sized carbon (CNT, CNF, Fullerenes)
Carbon Powder and Film

Preparation of Composite
Carbon and Pitch
Polymer
Metal
Ceramic

FormingHeat treatment

Carbon Growth on the Substrate4

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More concrete connections with raw materials to FCs
C1~C3 exhaust Gas

Starting Materials

C10+

Coal Tar Pitch

De-metallization
De-H2S

Studying Points

Qi, Ashes removal

Purification
Catalytic Pyrolysis

Halogen Treatment

Hydrogenation

Carbon nanofiberHigh MP IP

High MP MP

CokingModifications

Spinning

E. Spinning

SizingStabilization

Activation

Carbonization
Graphitization

Final Objects

MPCF

GPCF

ACF

CNFs

Needle cokes
Activated cokes

Light Weight

Electric
Desalination

Air Pollutant
Removals

Fuel Cell
Electrodes

Battery, Capacitor
Electrodes

Iron Smelting in Electric Arc Furnace.
Needle Coke Electrode.

Carbon blacks
Activated Carbons
Carbons for Nuclear

5

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Ｆｉｇ．３ CNF-ACF複合体を利用した複合体を利用したSO2連続除去プロファイル
連続除去プロファイル
複合体を利用した

ピッチ系活性炭素繊維100
紡糸

不融化

活性化

高表面積、ミクロポア、繊維状、導電性

問題点：吸着量、連続吸着、選択性
原因：ポア構造、大きさ、表面特性

Ｃ/Ｃ０（％）

等方性
ピッチ

OG15A-AS80

OG15A-H1100

60

OG15A-CNF20min-H1100

OG15A-H1100を利用した
硫酸回収型排煙脱硫装置は、パイロットテストを終え、2004年4月から実証Ｐｌａｎｔ稼動（九大－三菱重工－大阪ガス）

OG15A-CNF5min-H1100

40200010203040時間（ｈ）-KOH 賦活：Nanoporeサイズ制御：キャパシタ
サイズ制御：キャパシタ 物性賦活：
画期的向上-1050℃℃熱処理：表面性質制御：DeSOx性能画期的
性能画期的
熱処理：表面性質制御：
向上-硝酸処理：表面性質制御：
硝酸処理：表面性質制御：Chloro-compounds除去
除去
硝酸処理：表面性質制御：
能向上

Carbon supports forheterogeneous catalysts
Carbon supports

Electron conductivity, Chemically inert, Highsurface area, Usable functional groups,
Processability, Cost, Long life, …

Activated carbon

High surface area, Chemically inert,Processability, CostCarbon black

Electron conductivity, Chemically inert, Highsurface area, Usable functional groups,
Dispersion property

GraphiteElectron conductivity, Chemically inert, Cost,Long life, high crystallinity, …

OG15A-AS: Pitch based as-prepared ACF from Osaka Gas
OG15A-H1100: Heat treated OG15A-AS at 1100oC for 0h
OG15A-CNF5min-H1100: Heat treated CNF-OG15A-AS composites(CNF生成時間：5分）

OG15A-CNF5min-H1100を利用し、を利用し、 OG15A-H1100
よりさらに高い排煙脱硫性能を達成した。
（完全脱硫：28時間以上、定常脱硫率：（完全脱硫： 時間以上、定常脱硫率：8５％
時間以上、定常脱硫率： ５％

CNF-ACF 複合体（OG15ACNF5min-H1100）の開発によって）の開発によってプラント容積を1/2まで縮小可能
プラント容積を まで縮小可能

さらに高い脱硫率を目指している

Carbon is key element for Batteries !!
②Dry Battery①Li-ion[Cheap][Easy Available][High capacity](+) : LiCoO2(-) : Carbon(Graphite)
Conductor :Carbon(+) : MnO2(-) : Zn
Conductor :Carbon③Ni-MH[High power][Total balance](+) : (Ni-Co )(OH)2(-) : Mm(Ni-Mn-Al-Co)5
substrate:Nickel and Carbon

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Fuel cells: Types

Small fuel cells

Anode

H2O
CO2Internal
reforming
H2,COH2O
CO2External
reforming
H2, CO2

H2O

O2(Air) SOFC
O2(Air)

MCFC (650 ℃)
CO32-CO2(Air)

MCFC

H2O

O2(Air)H2O

O2(Air) PEFC/DMFC

AFC (70 ℃)
OH-

PAFC

O2(Air) AFC(CO2 removed)

Automobile Model of the Next Generation

ピッチ系高性能炭素繊維
不融化

SOFC (500-1000 ℃)
O2-

PEFC/DMFC (RT-80 ℃)
H+

H2

紡糸

CathodePAFC (200 ℃)
H+External
reforming
H2, CO2or CH3OH

メゾフェーズ
ピッチ

Electrolyte

Least Consumption of Clean Energy
Safe and Comfortable for Passengers and Pedestrians
Cleaning the Atmosphere through Driving
Carbon Composites of Highest Efficiency

炭化・黒鉛化

高弾性、高引張強度、高熱・電気伝導度
Light Body

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

Air Cleaning

Driving Control
Display

Battery, Capacitor

Safe Cage for Driverand Passenger

Adsorptive Temp. Cont.
Humidity Control

Fluorescent Paint

Shock Absorber(Electro Magnetic
Viscosity)

Atmosphere Cleaning
FilterPleat構造
構造 ＞ 均一・縮小 ＞ 圧縮強度向上Carbon Disk Brake

Shock Breakable
Bonnet / Engine Roomfor Safety of Pedestrians

Hydrogen Storage
Light Wheel /Transmission

Functional Glass(Transparent / Strengthened,
Thermal Conductive IR andEM Blind for Window)

Solar Cell,
Solar Reflection,
Heat Release

Thermo-TransferringFluid(Cooling and Heating)

Fuel Cell7

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Nuclear Energy

Carbons for Plain Water(High Temperature Gas Reactor)
He
Coal
Gasification

TurbineSteamTurbine(Steam)CO, H2

Hot Water
Reactor wall

C/C composites

New design

Heat exchanger

Best carbon

New system

Low temperature heat pu
mpBest carbon

New design

Heat transporter fluid

Nanofluids

New design and system

Implantation and Growth for 2 Weeks
Carbonized GFRPGFRP• Energy Storage: Battery, EDLC
• Heat Pump, Heat Sink
• Desalination• Filtration : Activated Carbons and ActivatedCarbon Fibers

Required Properties for Useful
Applications
As a carbon : General properties of bulk carbon
 Electrical and thermal properties
 High mechanical properties
 High surface area, porosity
 Graphitization properties
 Chemical properties as a carbon

SteelConcrete
As a nano-materials
 Nano size effect Regularity effect Quantum effect8

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Carbons & Nano-carbons
CarbonStructure Link
Analyses of Each Substrates

Assembly of nano, meso, macro-structuresat their Atomic to Bulk Sizes
Making nano-size

Mechanisms of Conversions
Nano-carbon

Catalysts and Structure Adjustments

Unit or Assembly of nano-units Size effect: Electron density in surface
 Regularity effect: Ultimate reactivity
 Quantum effect: Change of electric state More free surface: A kind of size effect Arranged free edge: A kind of regularity

Organic Feeds

Carbonization

Graphitization

CarbonNano-structure

Constituent
molecules
IR, NMR, ·····
Indirectly
observed

AssemblyClusters
XRD Analysis(d002, Lc, La)
Indirectly
observed

Graphite

Meso-structure

Assembly

Microdomains
HR-SEM, HR-TEM
STM, AFM

Assembly

Domains
SEM, Optic
microscope

Assembly

Bulks
Naked Eye ···Spherical,
Fibrous,
Flaky-shaped
Carbonaceous
materials
Carbon sheets :structural units

Nano
Technology

Nano, meso, microstructures9

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Design and Its Thermal Changeof Aromatic Stacking

Molecules in Mesophase Pitch
Naphthalene Pitch

methyl-Naphthalene
Pitch

dimethyl-Naphthalene Pitch

Models of mesophase constituent
molecules

Typical mesogen units in various
mesophase pitches(Mochida et al. Carbon 1990, 28,311)

200400600

8001000

1200

1400

1600

1800

TOF-MS spectra of synthetic
mesophase pitches

2000

Molecular Models
Spider Wedge Stacking of mesophase pitch(Zimmer et al. Advances in Liquid Crystal, New York,1982, 5)

Melt-XRD analysis
Change in Lc of mesophase pitch at higher temperature; (a)methylnaphthalene-derived pitch; (b) petroleum-derived
mesophase pitch; (c); coal tar derived-mesophase pitch; (d)naphthalene-derived mesophase pitch; (e) anthracenederived mesophase pitch(Korai et al. Carbon, 1992, 30, 1019)

ガラス炭素（GlassyCarbon)
ガラス炭素（Nano-structured carbons
Resin

硬化

熱処理

加工・後処理Bulky or particulated carbons having nano-structures

熱・電気伝導性、耐腐食性、高強度、ガス不浸透性

Activated carbons

問題点例）放電加工用電極 >>半導体
半導体Wafer上の汚れ
上の汚れ
半導体

Carbon aerosols or xerosols

原因：加熱放電時熱振動によるミクロドメイン粒子の落ち

Mesoporous carbons from mesoporous templated materials
Mesophase pitch-based carbon fibers, Glassy Carbons, C/C composites

Nano-phased carbons
Carbons having tens or less nano-scaled dimensions
Carbon nanotubes
Carbon nanofibers●高純度の炭素製品>金属系不純物元
素に よる汚染なし●プラズマによる材料消耗を少なく、長寿命●●フッ硝酸で、洗浄しても材料自体の消耗な しCarbon nanocell, Fullerenes
Pyrocarbons, and Carbon blacks

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Phase of reaction
Heat treatment
Temperature
(oC)

Vapor

Solid

LiquidOrganic materials

Structural units
MolecularStructures

Cluster

500
CokingFrom
Fromsolid and liquid
vapor phases phases

Partialmerger
Nucleation of Microof cluster
domainsLa
increasing

Solid

LiquidRadicalPyrolysis
Crosslinking

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

Decreasing
Shrinkage ormicrosporesmetamorphosisof microdomains Shrinkage ormetamorphosis
Lcof domains
increasing

600
Activatedcarbons
GlassyNeedleor hardcokecarbons Carbon
fiber(HT)DLC

Aromatization
Polycondensation

500
Carbonaceous
materials

Coking1000
CarbonMaterials
1500

2000

2000
Glassy Carbon
carbons fiber(HM)

Lc(112)increasing

3000

ElectrodeLibattery C/C

흑연화

흑연화

Graphites

Chemical andPhysical changes

Gas
volatilization

Molecular
Structures

Organic materials

탄화

탄화
1500

Phase of reaction
Vapor

200

1000
CarbonMaterials

Heat treatment
Temperature (oC)

Carbon materials

Carbon materials

600

Carbonaceousmaterials

Applications
Pore탄소화탄소화Aromatization
PolyconCrosslinking
densation

DomainMicrodomains
rawmaterials

Organic materials

200
RadicalPyrolysis

Microdomain

Graphites

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 start
Loss of viscosity (Inorganic Mat.)

H2
CO, CO2
H2Setc.

Removal of heterogeneous atoms
Dehydrogenation
Micropore nucleation
La increasing

H2SHCNCS2
N2 etc.
H2H2S
N2 etc.

Removal of heterogeneous atoms
Lc increasing
Reducing micro pores

Removal of inorganic materials
Formation of 3 D graphitic structure

3000

HOPG

Franklin Model of Carbon

Franklin’s Models of Carbon Structures

Cluster (Microcrystalline unit carbon)

arrangement

Graphitic
Intermediate
Non-graphitic

Angstrom- and Nano-scopic Views of Current Carbons
1. Three Dimensional Arrangements : Fibers, Needle Coke, Glassy Carbon(Carbon Shape)
2. Regions of Uniform Arrangement : Nano-Domain → Microdomain → Domain(Structural Hierarchy)
Optical Texture
Microfibril→ Fibrils

3. Variety of Cluster : Single, Double, Triple, … Layers
Size - Nano to Several Meters
Nano-Carbons and Their Units
4. Graphene → Hexagonal Sheet(Size and Shape)

Inter-unit Spaces: Voids, Defects, and Vacancy

11

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Nanoscopic Structure ofMesophase Pitch Based Carbon Fiber(a) Jenkins-Kawamura Model(b) Shiraishi Model

Structural models of turbostratic carbon

Structure of MCMBTEM Images of Hongye Anthracites Heat
Treated at Various Temperatures12

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Assembly of Carbon Nano-rods

Lithium Ion Battery, Electrode
Lithium ion insertion sites of carbon

Activated CarbonSurface Oxygen Functional Groups of AC

Images of comprehensive structure of pores
Pore

Inner surface
Outer surface

Wall

Sub-micro pore
< 0.8 nmMicro pore
0.8 ~ 2.0 nm
Meso pore
2.0~ 50 nm
Macro pore> 50 nmClassification of surface and pores

Schematic shapes of pores

Bulk Carbon Wall13

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Super-capacitor (or Ultra-capacitor)

Capacitor
Insulator

Understanding carbon structures：：Carbon nano-world

Nano

Separator

Productions

Applications

Structures+–+–• Structural units• Nano-phased units

SpacesElectrodeElectrode

Q = C·V

W = 12 C·V2Q : charge in coulombs
C : capacitance in farads
V : voltage in volts
W : energy in joules
V : voltage in volts
C : capacitance in farads

Capacitance(C) is a measure of the amount ofcharge(Q) stored on each electrode for agiven potential difference or voltage (V) whichappears between the plates.

Activated carbon etc.

Electrochemical doubledouble-layer capacitors (EDLCs)
The electrodes are made of carbon materials, which has ahigh surface area per unit volume, further increasing thecapacitor's energy density.

PseudoPseudo-capacitors
The electrodes are made by transition metal oxides, eg.
RuO2, IrO2, NiO, etc. Electrodes made by metal oxides store
the charges by two mechanism: double layer effect andpseudocapacitance by faradic redox reactions

炭素物質の分類• Pore sizeand homogeneity• Pore amounts+Surfaces

Controls
Syntheses
Hybridization→→
Improving
Improving
MassPerformances
Performances
productionand Functions

High
performancesHighfunctionsand→Functions
Creating

New Functions• Edges(Kinds and amounts)• Basals(Perfectness andOrientation)

Newfunctions

GraphiteとGraphene5556

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炭素物質の相図

Graphiteの構造

5758

Graphiteの電子状態

Graphiteの反応性
ＧｒａｐｈｉｔｅのＦｉｒｓｔ Ｂｒｉｌｌｏｕｉｎ ｚｏｎｅ
は、六角柱形状
Ｂａｎｄ構造：ＥＦ値をＺｅｒｏ、Ｋ←Γ方向に沿って、K点でＥＦに集まってくるように見える4本の線がπＢａｎｄ（Ｇｒａｐｈｉｔｅ準位セル中に4個の炭素原子）πＢａｎｄの内、π2とπ3はK→Ｈ区間では縮退し、ＥＦ交差する。この状態を拡大した図が（ｃ）である。Ｋ→Ｈ区間で縮退したπ2とπ3のＢａｎｄ計算値は0.028eVであり、これはＨＯＢａｎｄとＬＵＢａｎｄの重なりと解析される。
以上のことから、ＧｒａｐｈｉｔｅではＥＦ近傍に電子と正孔が導電キャリヤとしてほぼ同数固発生し、半金属と呼ばれる挙動をする。電子のフェルミ面はＫ点付近、正孔のそれはＨ点付近にある。
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How to prepare graphene?

フッ化Graphite

Three major methods:
Micromechanical exfoliation from graphite
K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang, Y.
Zhang, S. V. Dubonos, I. V. Grigorieva, A. A. Firsov,Science 2004,
2004 306, 666.
Meyer, J. C.; Geim, A. K.; Katsnelson, M. I.; Novoselov,K. S.; Booth, T. J.; Roth, S. Nature 2007,
2007 446, 60.

Epitaxial growth by Chemical Vapor Deposition
Reina, A.; Jia, X. T.; Ho, J.; Nezich, D.; Son, H. B.; Bulovic, V.;
Dresselhaus, M. S.; Kong, J. Nano Lett. 2009,2009 9, 30.
Kim, K. S. Nature 2009,2009 457, 706.

6261

1. Preparation of graphene discs

1. Preparation of graphene discs

Preparation of uniform graphene discChemically derived graphene via exfoliation and reduction(1) Isolation into graphene oxide
Oxidation

graphitexxxxxxxxxx
graphite oxide

Sonication

xxxxxxxxxx

Step-by-step cutting of graphenes of platelet carbon nanofiber (PCNF)
PCNF consists of nano-sized platelet structuralunits stacked perpendicular to fiber axis.
The plate unit has the thickness of 2-3 nmconsisted of 6-10 graphene layers.

isolated graphene oxides

The chemical reduction method is a suitable approachto producing graphene sheets in bulk quantity at relatively low cost.

Graphene(2) Reduction to graphene

However, preparation of graphene with defined shapeis still a challenging work.

graphene oxide

PCNF

Structural unit

Yoon SH et al. Carbon 43,43 1828 (2005).

Reduction

graphene

6364
Cutting to structural unit, and then graphene16

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1. Preparation of graphene discs

Grapheneの電子状態と電子物性

Chemical reduction of GPCNF oxide
Hydrothermal reduction using NaBH4 at 130oC for 5 hOxidation

K/GP = 1xxxx Sonication
xx

K/GP = 3xxxx
Reduction
xx

K/GP = 5

Ｐ点で現れるＥＦにおいてπ性のＨＯ及びＬＵＢａｎｄは、近似的に言えばほぼ直線的に交わる。Ｆ
ｅｒｍｉ準位では両Ｂａｎｄは接するだけで、絶対零度での状態密度はＺｅｒｏである。これを立体的に示すと（ｃ）のようになる。これをＤｉｒａｃ型円錐とよぶ。
磁場下での二次元分子運動の性質から由来する分数量子ホール効果と振動磁気抵抗効果も示す。
量子電気力学の立場からすると、Ｇｒａｐｈｅｎｅの電子は実効的に相対論的な波動方程式であるＤｉｒａｃ法的式に従い、質量がない粒子（Ｄｉｒａｃ型Ｆｅｒmi粒子）として考えられる。Ｇｒａｐｈｅｎｅにおける電子の速度は光速度の程度まで大きい。
66

K/GP = 6 65

Graphene Fragment

Polyacene

6768172011/10/28Polyphenanthrene

PAとPPhの結晶軌道相

69

カルビン

70

カルビンについての計算データ

717218

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カルビンの合成

Diamond合成

7374

Diamond構造

Diamond

正四面体型のダイヤモンド構造：面心立方格子
炭素間距離：0.1544nm、結合角度：１０９．２８°
再隣接原子数：４、第二隣接原子数：１２立方体１辺の長さa0:0.3567 nm
空間群：O7h (Fd3m)
窒素やホウ素の混入が多い。
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Diamondの電子状態

Diamond77

Diamondの化学反応性(a) Diamondのバンド構造は(a)に示す面心立方構造の逆格子空間を参照しながら行う。
(b) Band Gapに関わる電子転移は、Γ点にあるHO Bandの頂上から、Γ-Ｘ間にあるＬＵBandの底に対する間接転移であることが、ケイ素の場合と似ている。
Ｂａｎｄ Ｇａｐの計算値は5.67eVであり、実験値は5.48eVである。この値からＷｉｄｅ ｇａｐを持つ半導体で、実際には絶縁体である。
ＩＩｂ型ダイヤモンドはp型半導体：0.37eVでＡｃｃｅｐｔｏｒ
Ｉｂ型（窒素を含む）n型半導体：ＬＵ Bandの底から1.7eVの準位でＤｏｎｏｒ78

Diamondの化学反応性

79

80

20

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Amorphous Carbon

Amorphous Carbon

81

Amorphous Carbon

82

Amorphous Carbon

83

84

21

2011/10/28

炭素の化学反応•

炭素の化学反応(ガス化反応）-•

気相反応：無触媒ガス化、触媒ガス化
液相反応：湿式ガス化反応、電気化学反応
固相反応：炭素還元反応、炭素生成反応
層間加工物生成反応

炭素のガス化反応：工業的に重要-

石炭の燃焼・ガス化
高炉のコークスのガス化
炭素質が付着した触媒の再生
活性炭素の製造＋- 炭素質の耐酸化性の改善

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