APR. 19, 2021
第2講義

炭素の合成
（機能性炭素材の製造法）

Seong-Ho Yoon
IMCE, Kyushu University, Kasuga, Fukuoka, Japan授業内容
1. 炭素の種類- 炭素質，炭素，黒鉛- 易黒鉛性及び難黒鉛化性炭素
2. 気相，液相および固相炭素化
3. 液相炭素化- ピッチおよび等方性コークス- 液相ピッチおよびニードルコークス
4. 気相炭素化- 炭素ナノ繊維の調製
5. 固相炭素化- バイオマスを用いたLi-ion電池負極材の調製
6．まとめ

Kyushu University UI project Kyudai Taro,2007

2

炭素材料
炭素材料：90％以上炭素によって構成された材料
人造炭素材料

天然黒鉛
108
Ag→
Cu→
Al→

107

105

炭素繊維

活性炭素繊維⇦ AsFs-黒鉛層間化合物(GIC)
105⇦ FeCb-GIC⇦⇦ K-Bi-GIC≈⇦ 自然黒鉛
高配向熱分解黒鉛 (HOPG)⇦ 黒鉛ウィスカ
⇦ 気相成長炭素繊維（3000oC)⇦ 黒鉛電極⇦ PAN系炭素繊維（3000oC)⇦ 気相成長炭素繊維

引
張 104
強
度

⇦ 黒鉛ウィスカ
⇦ 気相成長炭素繊維（3000oC)⇦ PAN系炭素繊維⇦ 気相成長炭素繊維

103

比
表
面
積

⇦ 産業用活性炭（700～1600 m2g-1）
商業用PAN系活性炭素繊維（500～1500 m2g-1）⇦
商業用Cellulose系活性炭素繊維（500～1500 m2g-1）
1,000⇦ 高密度等方性黒鉛⇦ 産業用ゼオライト（400～750 m2g-1）⇦ Pitch系炭素繊維⇦ 産業用シリカゲル（250～600 m2g-1）⇦ 産業用アルミナゲル（150～350 m2g-1）⇦ PAN系炭素繊維

黒鉛電極

商業用Phenol系活性炭素繊維（900～2500 m2g-1）
商業用等方性PITCH系活性炭素繊維（750～2500 m2g-1）

2,000⇦ ガラス状炭素（3000oC)⇦ ガラス状炭素（1000oC)
104

活性炭

3,000

⇦ 黒鉛（単結晶）/m2g-1

・

ガラス状炭素/Mpa/S m-1

電
気
伝
導
度 106

人造黒鉛

100

電極材

複合材

スポーツ用材料

キャパシタ

吸着材

3

1.炭素の種類- 炭素質，炭素，黒鉛- 易黒鉛性及び難黒鉛化性炭素

炭素基礎（多様な炭素同素体）

4炭素同素体の炭素-炭素結合56What is the synthetic carbon!
Origin of Structural Units And Crystalline Defects
Heat treatment

Organic materials
Basic structural units
2 ~ 10 nm

CarbonMicro domain

Orientation
Rearrangement

Coagulation
Partial melt fusion
DomainGas
LiquidSolid

4 ~ 6 nmModified Structures

Carbon or carbonaceous materials

Varieties of structural unit
Heat treatment

Heat treatment of organic materials
RT

100℃

200℃

300℃

400℃

500℃

600℃

700℃ 800℃

Aromatic organic
materials

Organic
materials

①

②

③
④

ΔH

⑤

900℃ 1000℃

Carbonaceous
materials⑥⑦

Reactions①②+

Removals of water and VMs+

Dissociation and removals of light organics③+

Dissociation and polymerization of organics④⑤+

Polycondensation of organics, dealkylation+

Coking⑥₋?

Dehydration and dehydrogenation, CO removal

⑤~ ⑥

+

Removal of sp3 bridged bonds

⑥~ ⑦

+？

Completion of polycondensation of intra-cluster units (Dehydrogenation),
Removal of alkyl groups, Removal of ultramicroporosity

5

Heat treatment of organic materials
Carbon materials

Graphite materials

1000℃

1200℃

1600℃

2400℃

①

②

③

④

ΔH

2800℃

3000℃

⑤⑥

Reactions①∼②‐？

Start of linkage with inter-clusters

②∼③

‐？

Linkage with inter-clusters, Removal of edge phase, almost removal of
microporosity

③∼➃

‐

?

➃∼➄

‐？

Construction of 3D structure maintaining domain structure, Complete removalof micro-porosity

➄∼➅

‐？

Completion of graphitic structure with removal of domain structure, HOPG
forming temperature89

有機物の加熱による変化
前駆体生成過程

炭素化過程

前期
低分子・高分子生成物 H2O, CO2, CH4, H2

黒鉛化過程

後期

化学における共役系（きょうやくけい、英: conjugated system）は、化合物中に交互に位置する単結合および多重結合に非局在化電
500℃
1000℃
1500℃
3000℃
子を持つ結合p軌道系である。共役系は一般的に、分子全体のエネ
ルギーを低下させ、安定性を高め
分解
炭黒前る。非共有電子対やラジカル、カル
共役系
組織の
構造再編
芳香族化
駆
拡大
緻密化
黒鉛構造発達 鉛
ベニウムイオンなども共役系の一重縮合体
素部となる。化合物は環状、非環状、線状あるいはこれらの混合物であ
る。
焼成工程
黒鉛化工程

10

温度や原料による人造炭素材料
熱処理
温度(oC)

気相

反応相
固相

材料
液相

気体

固体または液体構造
クラスター 細孔

原料：石炭、ポリマー
石油、バイオマスなど
200

熱
処
理

ラジカル
熱分解

芳香族化
重縮合

架橋
500

600

炭素質材料

炭
素
材
料

コーキング

1000

炭
化

炭素材料
1500

熱分解炭素
(コーティング
C/Cなど)
活性炭
繊維状
炭素
ガラス状 ニードル
ダイヤモンドまたハード コークス
状炭素
炭素
炭素繊維
(高強度)

La増加
マイクロ細孔の
減少

Lc増加

ガラス
炭素

2000

黒
鉛
化 3000クラスターの核形成
マイクロ細孔の
核形成

人造黒鉛

電極
HOPG

炭素繊維
(高弾性率)
Li電池 C/C
複合材

Lc(112)増加

Heat treatment
Temperature (oC)

Phase of reaction
Vapor

Solid

LiquidGas
volatilization

Chemical andPhysical changes

Organic materials
200
탄
소
화

RadicalPyrolysis

Aromatization
Crosslinking

Polycondensation

500

Carbon materials

600

Carbonaceous
materials

Coking1000
탄화CarbonMaterials
1500

2000
흑
연
화

Graphites
3000

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 start
Loss of viscosity (Inorganic Mat.)

H2
CO, CO2
H2S
etc.

Removal of heterogeneous atoms
Dehydrogenation
Micropore nucleation
La increasing

H2S
HCN
CS2
N2 etc.
H2
H2S
N2 etc.

Removal of heterogeneous atoms
Lc increasing
Reducing micro pores

Removal of inorganic materials
Formation of 3 D graphitic structurePhase of reaction
Heat treatment
Temperature
(oC)

Vapor

Solid

LiquidOrganic materials

Structural units
Molecular

Structures

Cluster

RadicalPyrolysis

Pore

From
From
solid and liquid
vapor phases phases

Aromatization
Crosslinking

Polycondensation

500

Carbon materials

600

DomainMicrodomainsrawmaterials

Organic materials

200
탄
소
화

Microdomain

Applications

Carbonaceous
materials

CokingPartialmergerNucleation of Microof cluster
domainsLa
increasing

PyroCarbons
Nucleation(Coatingof domain
Nucleation C/C etc)
by mergerof microof microporesdomains
Fibrouscarbons

1000
탄화

CarbonMaterials
1500

Decreasing
microspores

Shrinkage ormetamorphosisof microdomains Shrinkage ormetamorphosis
Lcof domains
increasing

Activatedcarbons

GlassyNeedleor hardcoke
carbons Carbon
fiber
(HT)

DLC

2000
흑
연
화

Graphites

Glassy Carbon
carbons fiber(HM)

Lc(112)increasing

3000

Electrode
HOPG

Libattery C/CFrom fossil fuel to functional carbons

Kyushu University UI project Kyudai Taro,2007

炭素の基礎（黒鉛の分子構造）14炭素の基礎（黒鉛の結晶因子）15炭素の基礎（黒鉛のXRDプロファイル）

16

17

人造炭素材料の構造理解

難黒鉛化性

黒鉛の基本構造

Turbostratic-構造
低結晶度

Graphitic-構造
高結晶度

炭素六角網面積層の配列

易黒鉛化性

Franklin モデル[1]XRDから 2次元

リボンモデル[2]シェルモデル[3]TEMから 3次元
[1] Franklin R E. Proc. Roy. Soc. London A, 1951, 209: 196[2] Johnson G M. Kawamura K, Nature, 1971, 231: 175[3] Shiraishi M, Kaitei Tansozairyou Nyuumon, 1984, 29

炭素の基礎（炭素の高次構造）

18

ドメイン構造との連携
DomainCluster(a) Non-Graphitizing (Isotopic)(b) Partially Graphitizing

Microdomain(c) Graphitizing

炭素の基礎（易黒鉛化性炭素と難黒鉛化性炭素）20
Non-graphitizable
Isotropic coke

Carbon from phenol resin

Feature• Non-graphitizable• Ball shaped domain• Domain ≈ Micro-domain
10 nm

Graphitizable
Anisotropic coke

Mesophase pitch based CF

Feature• Graphitizable• Linear shaped domain• Domain > Micro-domain
10 nm

Domain of NGC has similar size and shape of micro-domain, whereas GC does larger
and much linear shaped domain than that of NGC

21

What is the synthetic carbon!
Origin of Structural Units And Crystalline Defects
Heat treatment

Organic materials
Basic structural units
2 ~ 10 nm

CarbonMicro domain

Orientation
Rearrangement

Coagulation
Partial melt fusion
DomainGas
LiquidSolid

4 ~ 6 nmModified Structures

Carbon or carbonaceous materials

Varieties of structural unit
Heat treatment

22

ドメインモデル
炭素材料の構造：分子～バルク
分子

クラスター

I. Mochida, et al., TANSO, 215, 274-284 (2004).

マイクロドメインドメイン（マクロ）

バルク

炭素材料
炭素繊維、活性炭、黒鉛など
IR, NMR, ∙∙∙∙∙∙
Indirectly observed

XRD Analysis
Indirectly observed

ナノ構造

HR-SEM, HR-TEM
STM, AFM

SEM, Optic
microscope

メソ構造

Naked Eye

マクロ構造

ナノ構造

メソ-構造

図。マイクロドメインとドメインモデルからメソフェーズピッチ系
黒鉛繊維の構造ヒエラルキー

23

先行研究
低い

比表面積
[m2/g]

537

賦活度が高くなるにつれて
1. ドメインサイズが減少
2. 表面外側から酸化3. 細孔の生成進む

764

ドメインとマクロ構造特性が密接な関係を確認した。

賦
活
度

低い

賦活度

高い

1050

高い

1873
Scheme. Proposed Models for the Pore Structure of ActivatedCarbons Based on the Microdomain Component

Fig. STM images of (a) OG5A, (c)OG7A, (e)OG10A, and (g) OG20A
Pitch-based activated carbon fiber

マイクロドメイン構造モデルに基づいて、賦活度に応じた細孔構造を説明した。
N. Shiratori, et al., Langmuir, 22, 7631-7637 (2009)炭素の基礎（ドメイン構造）24

2. 気相，液相および固相炭素化

炭素化（Carbonization）とはKyushu University UI project Kyudai Taro,200726

炭素材の製造例

3. 液相炭素化:• 等方性ピッチおよび液相ピッチ• ニードルコークス

液相炭素化••

液相炭素化（Liquid phase carbonization）: 液相を経由する炭素化．炭素化反応が液相中で進行するため，分子の移動や配向が起こり易い．熱溶融性の有機物前駆体を，常圧下300～
500℃程度に熱処理して得られる生コークスのほとんどは易黒鉛化性炭素である．液相炭素化する前駆体としては，石油や石炭タールの精製残渣としての重質油やピッチ，ポリ塩化ビニ
ル等の熱可塑性高分子，アセナフチレン，デカシクレンなどがある．これらの前駆体は一般には炭素化反応中に極めて高分子量の平面性芳香族化合物を生じ，それらを構成成分としてメ
ソフェーズを生成する．メソフェーズの組織や発達の程度によって，高温処理後の炭素材料の黒鉛化度が支配される．そのため，この段階におけるメソフェーズの制御が重要で，前駆体の選択やフリーカーボンの除去，炭素化条件などが工夫されている．
縮合：- 脱水素縮合（Dehydrogenative condensation）：パラフィンの脱水素環化芳香族と芳香族化合物の縮合は通常，脱水素を伴って進行する．これによって炭素化収率，軟化点が向上する．
熱的に加えて接触的，炭素化的な脱水素縮合も進行し，工学的にも応用されている．エアブ
ローは酸化的脱水素縮合の代表例で，鋪装用アスファルトや活性炭素繊維や粒子の原料ピッチ製造に応用されている．このほか，アルカリ金属，ヨウ素，遷移金属塩化物，酸化物等の脱水素複合剤も知られている．
-非脱水素的縮合（Non-dehydrogenative condensation）：分子量の小さい成分や重質油は，縮合反応によって重質化されることにより炭素化性を変えることができるが，この際，水素を脱離しない場合を非脱水素的縮合という．例えば，AlCl3を用いるとその低温での縮重合促進効
果は，コークス収率を上げることからも明らかであるが，減圧残油の軟化点を比較的に低く押さえることもできる．これは水素を脱離せずに芳香族の縮合が進み，縮合と同時にナフテン環を形成することによると推定できる．HF/BF3は金属腐食性の超強酸であるが，回収の容易な
極めて強力な酸としてナフタレン等の種々の芳香族化合物を200～300℃の温度で非脱水素的縮合化を進め，高純度のメソフェーズピッチの直接合成に利用できる．

触媒による法構造物質の縮重合

Catalytic condensation ofaromatic hydrocarbon
with HF/BF3

Scheme of catalytic polymerization ofquinoline and isoquinoline with AlCl3

ピッチ

31

ピッチ（Pitch）:木材，石炭などの乾留の際に得られる液状タール，オイルサンドから得られるビチューメン，オイルシェールの乾留によって得られる油分，原油の蒸留による残渣油，石油留分のクラッキングによって生成するタールなどを熱処理，重合して得られる常温で固体状のものの総称．工業的には石炭系ピッチ，石油系ピッチが重要である．
最近ナフタレンなどの芳香族化合物を重合した合成ピッチも製造されるようになった．
ピッチは化学的には無数の縮合多環芳香族化合物の混合物で，平均分子量は300～
1000程度の範囲にある．350～450℃程度の温度で熱処理すると光学的異方性組織（メソフェーズ）の炭素質液晶が発達する．メソフェーズの組織構造（テキスチャー）はコークス，炭素材料の特性をほぼ決定してしまうので，ピッチの化学構造，熱分解ならびに重合挙動を知っておくことはきわめて重要である．分子量，分子量分布ならびに
NMR，IRから求められる化学構造指数（例えば芳香族炭素分率，縮合環数など），粘度などが測定される．

ピッチの高分子やオリゴマー等の有機化合物との違い
1．多環芳香族の混合体: 5000種以上の多環芳香族物質が混在
2．軟化点が高くなるにつれ，溶媒に溶けない成分がある．
3．炭素繊維前駆体ピッチなどの可溶性高軟化点ピッチは，ピッチの中で溶媒不溶成分と溶媒可溶成分が混在 → 溶媒成分の役割をする成分がある．
4．すでにある程度積層クラスター構造を形成している．
5．軟化点以上になれば，溶媒成分の積層は解体され，溶質成分を分散させる．液晶
ピッチは可溶状態でも積層クラスターをもつ．

等方性および液晶ピッチ•••

等方性ピッチ（Isotropic pitch）： 縮合芳香族化合物を主成分とする石炭系，石油系のタール
ピッチ，ナフタレンのような化合物から合成されたピッチは，分子または分子の集団（ラメラ）が無秩序に配向しているために偏光顕微鏡で観察しても光学的に等方性である．このようなピッチを加熱処理すると光学的異方性を示すメソフェーズが生成する．
メソフェーズピッチ（Mesophase pitch）: メソフェーズを含むピッチ．メソフェーズは偏光顕微鏡に
より光学的異方性を示す組織として観察されることから，メソフェーズピッチは異方性ピッチとも言われる．異方性部分の分子配向に起因して，高温熱処理により容易に黒鉛化が進行する典型的な易黒鉛化性炭素で，重要な炭素原料の一つである．特に，繊維軸方向に沿って炭素網面が配向したピッチ系高弾性率炭素繊維の原料としての研究が進展した結果，メソフェーズ
ピッチの調製や評価の技術が飛躍的に発展した．炭素繊維用メソフェーズピッチは，石炭系あるいは石油系タールピッチを適当な条件下で熱処理し，これに溶剤抽出，水素添加を組み合わせて調製される．超強酸を用いてナフタレンやメチルナフタレンなどを重縮合させる調製法も開発された．
ニードルコークス（Needle coke）：針状コークスと同意語で，1940年代にアメリカで製造された石油コークスがたまたま金属光沢を有し，外観上
細長く針状（Needle like）を呈していたことに由来する．別名No. 1コークスあるいはプレミアムコー
クスと称され熱膨張係数（CTE）値が低く強い異方性を有する点に特徴がある．顕微鏡観察によると配向繊維状組織（Fibrous texture）を示し，
流れ模様にそって炭素六角網面構造がよく発達
ニードルコークスの外観（a），組織（b），構造モ
して黒鉛化し易い特性も有している
デル（c）（持田勲：炭素材の化学と工学，朝倉書店（1990）p.231．）光学的等方性ピッチを熱処理する際，異方性ピッチ化される過程

33

ピッチへの積層構造
原料

脱QI

球晶生成

バルクメソフェース

球晶成長・合体

バルクメソフェース

加熱

球晶生成

35

液晶ピッチの分子構造

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)

TOF-MS spectra of synthetic
mesophase pitches液晶ピッチの積層構造

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)

36

Carbon Industry – Chain Industry

39

EOとCTの元素分析，13C-NMRおよびTOF-Mass分析
13C NMR analyses

Elemental analyses
Rawmaterial

EO

C
H(wt%) (wt%)

92.30

CT

92.58

7.41
5.96

H/C

0.96
0.77

N
(wt%)

0.00
0.84

Aliphatic (%)
Car1,30.62

fa

Car1,2
Car3/Car2

CH3

CH2

Cchain CHar Car3

Csar

EO

9.0

10.2

6.4

19.3

9.7

7.8

37.6

0.26

0.74

CT

1.1

10.6

1.9

1.3

24.3

2.1

58.7

0.41

0.86

0.14

CT
Mw330

EO
Mw200

Aromatic (%)

S
(wt%)

Car2

✓CT has more heterogeneous atomic compounds
than EO✓fa: 0.86✓Mw: 200～500 (300～400)
0

100

200
300
400
Molecular Weight （m/z)

500

600

TOF-MS of CT

40

GC-AEDを用いたEOの環数分布
GC-AED
C-AED Response (count)

1200✓ EO: 90％ of 1～2 six membered rings

EO

1000

- Many Alkyl Naphthalene

800
600
400

Model compounds of EO

200
0

2

4
6
8
10
Retention Time (min)12

Molecular compositions of raw materials
Ring number
EO
1-Ring46.7
2-Ring43.9
3-Ring5.5
4-Ring3.5
5-Ring0.4>5-Ring
0.0

14

MW:210

MW:182

MW:184

MW:12841

GC-AEDを用いたCTの環数分布
GC-AED

C-AED Response (count)

1200
1000

NCO

✓ CT: 2～4 six membered rings

800

CT

✓ Almost 2 and 3 membered rings

600

Model compounds of CT

400
200
0

2

4
6
8
10
Retention Time (min)12

MW:316

14

Ring compositions of CT
Ring number
1-Ring2-Ring3-Ring4-Ring5-Ring>5-Ring

NCO
46.7
43.9
5.5
3.5
0.4
0.0

CT
0.0
31.3
27.3
22.2
5.2
4.0

MW:340
MW:36642

2-MNのBromination-dehydrobromination反応
Process

NMR analysis

2-Methlynaphthalene(2-MN)

Br
Ar-CH3

Halogenation(Br2：the same amount with2-MN)@30～180oC

Bromination of
2-MN
Aging
@320oC

Bromo-methyl naphthaleneBr
Ar-CH3Br

1-bromo-2-methyl naphthalene
Ar-CH3

2-Methylnaphthalene

Pitch
9

8

7

6

5
4
3
Chemical Shift(ppm)

2

1

0

43

合成したピッチの分子量と分子構造
13C NMRTOF-MSLASER
Nd:YAGLASER intensity
45%
Mass range
10 ~ 1000
Measurement Mode
Spiral type

Dimer
282
Trimer420

Aromatic
pitch

Tetramer
556
695

200

300

400

500
600
700
Molecular Weight （m/z)

833

800

973
900

1000

C1

C2

Aliphatic
fa

C3

C4

C5

MN10

15.57 18.19 58.40

5.15

2.70

0.92

MN15

14.92 18.30 58.98

5.70

2.10

0.92

MN20

16.33 18.23 57.18

6.28

1.98

0.92

2MN

9.09

0.00

9.09

0.91

18.18 63.63

C1: 132.5-149.2ppm, substituted carbon
C2: 129.5-132.5 ppm, outer quaternary carbon
C3: 115-129.5 ppm, unsubstituted carbon
C4: 22-53 ppm, methylene carbon(methylene bridge)
C5: 22-11 ppm, methyl carbon(CH3)
fa: carbon aromaticity
持田勲、炭素材の化学と工学、1990、p60
Diaz C, Blanco CG. Energy & Fuels, 17,(2003) 90744合成したピッチの代表的な分子構造
Dimer
282

Pentamer
695

Trimer422

Hexamer
833

Tetramer
558

Heptamer973

45

メチレン架橋による重合機構

46

Dehydrobromination/polycondensationの際の (a) Scheme ofdehydrobromination/polycondensation; (b) Isothermal dehydrobromination kinetic
curves; (c) Arrhenius plots of lnk and 1/T for the thermal dehydrobromination of M-Br.

47

NCBとNBの代表的な分子構造

NCB

NB
MW 636

MW 812

MW 1134

MW 1191

MW 1412

MW 96248

49

Characteristics of needle coke
Graphite electrode=

Needle coke + Binder pitch
Impregnation pitch

Prerequisite of Needle Coke
1. Low CTE
2. Low Puffing
3. High Strength of Grains
4. Good Wettability⇒
How to achieve above properties ?

Manufacturing Graphite Electrode50

51

黒鉛電極の製造
Anthracite

Graphite

Coke
Binder
Pitch

Silos

Crushing
MixingForming

Screening
Grinding

Storage bins

Pitch
Impregnation
BakingClassified
Fractions

Weighing
Graphitization

Machining

Finishedproduct

等方性黒鉛の製造工程（二元系原料）52

Flow of coal tar related materials

重質油を用いたカーボンサークル

54

Flow of coal tar related materials

56

Preparation of carbons

What is the most important for carbon manufacturing?
• Specific properties of target material.
ex) Carbon fiber➢ Tensile strength: impurity, surface property, molecular orientation➢ Modulus: molecular orientation, graphitization degree➢ Elongation property: selection of raw material, heat treatment temperature➢ Thermal conductivity: graphitization degree• How to achieve such properties?
ex) Carbon fiber➢ Tensile strength: low impurity, amorphous surface property, highmolecular orientation➢ Modulus: high molecular orientation, high graphitization degree➢ Elongation property: precursor control, low temperature heat treatment➢ Thermal conductivity: high graphitization degree

先端炭素材の製造におけるポイント

57

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…

58

Purification of raw and precursor materials• Advanced functional carbons always require higher than certain levelof purification.
• Kinds of impurities are very dependent to the target materials.
- In the case of needle coke: Sulfur and nitrogen compounds
are important impurities.
• The purification of functional carbons almost rely on the purity of ra
w and precursor materials.
• The optimized purification method is very dependent to the raw mat
erials, size of manufacturing and production cost.
- Pitch-epoxy : Centrifugation method- Needle coke : Solvent-non solvent method- FCC-DO: High temperature centrifugation (several times)• To find out the optimized purification method of raw or precursor ma
terials is most important key technology in the functional carbon pro
ductions.

59

Method① Filtering(Heat, Solvent)Principle
Decreasing viscosity byheating or solution
Mesh filtering of QI② Centrifuging(Heat, Solvent)Decreasing viscosity byheating or solution
Centrifugal condensing of QI③ Solvent Precipitation

Mixing of miscible solvents
Precipitation removal of QI④ Non-solvent
Precipitation

Mixing of non-miscible
solvents
Precipitation removal of QI

Advantage

Disadvantage

Only QI Removal
No heavy fraction
removalLarge equipment X

Only QI Removal
No heavy fraction
removalLarge equipment X

Low productivity

Large equipment
OK

Heavy fraction
removal• It is relatively easy to remove QI in lab scale.
• QI removal in the industrial scale➢ Very difficult to remove finely dispersed QI from large amount of viscous liquid➢ Only success in Japan
Japan several ten thousands ~ hundreds tons/year scale

Stationary method60

QI removal from CT
Solvent-Non-solvent method

ＱＩ成分
ＣＴ成分

（１）CT is dissolved into solvent（２）QI is precipitated by the addition of nonsolvent（３）Pitch phased precipitate is removed.

Solid – liquid separation bydecantation *Time &Temperature

61

Phases of precipitate (QI+?)
Phase changes of precipitates
Kerocenew%

Precipitate
w%

10
10
10
10
20
20
20
30
40
40
50
60

80
60
40
20
60
41
20
60
40
20
40
20

10
30
50
70
20
39
60
10
20
40
10
20

38.7
45.5
37.2
40.2
24.8
17.1
-

0.0

2

1.0

1

5

3

Ke
ros
ene

Wash oil
w%

oil
sh
Wa

1
2
3
4
5
6
7
8
9
10
11
12

CT
w%

0.5

6

SLURRY
ZONE

0.5

8

OILY
CRYSTAL ZONE
ZONE

9

4

1.0

PITCH ZONE

0.0

0.5

CT 7

0.0
1.0
10

OILY
・・・No solid precipitate, difficult to separate
SLURRY ・・・Easy to separate but large amount ofprecipitate
CRYSTAL ・・・Difficult to separate
PITCH
・・・Small amount of precipitate, easy to separate

62

Adjustment of removal conditions
②

①

③

④

⑤

⑥

Changes of precipitate amounts of CT under various conditions
Kerocene

30
30
30
30
30
30

26
24
22
18
16
14

44
46
48
52
54
56

Precipitate (%)
QI (%)
①
23.6
2.15
②
23.6
2.16
③
10.36
2.35
④
11.5
2.64
⑤
18.2
2.54
⑥
30.1
2.50

0.0

Ke
ros
ene

Wash oil

OILY
ZONE

0.5

Easiness of decatation
QI amount ≈ Precipitate amount
Kind of solvent, Mixing ratio
Temperature, and time

SLURRY
ZONE

1.0

oil
sh
Wa

①
②
③
④
⑤
⑥

CT

0.5

CRYSTAL
ZONE

1.0

PITCH ZONE

0.0

0.5

0.0
1.0

CT

63

Understanding raw and precursor materials• To select and design the target functional carbons, fullunderstanding of raw and precursor materials arenecessary.
• It is not still enough to understand the molecular
structures of raw and precursor materials.

• It is strongly required that the novel analytical method toanalyze the detailed molecular structures of raw andprecursor materials.
• TOF-MASS, GC-GC (2D), GC-AED, etc.
• It is also strongly required that the novel analyticalmethod to analyze the detailed impurity structures of raw
and precursor materials.
• Chelated structures of Ni and V in DO materials, etc.
64

65Properties of high performance binder matrials
Property
Softening point(Ring & Ball method) (oC)
Density (25 oC)
Coking value (%)
Benzene Insoluble (%)
Quinoline Insoluble (%)
C/H (Atomic ratio)
Temperature appearing
500 cP (oC)

Required level
80 -1101.28 – 1.32
55-65
30 – 35
10 -161.70 – 1.85

150 – 180

Some properties of binder and impregnation
pitches

66

100%

100

100

80%

I
P

60%

PI

40%

TI-THFS
HI-TS

60
wt%

THFI-PS

B
P

80
60
wt%

80

40
20

40
20

20%
HS

0
100

0%

IP
Fig. 3.1

BP

I
P

HPLC analyses of binder and impregnation pitches

500

600

0
100

200
300
400
Temperature (℃)

500

600

Fig. 3.1 バインダーピッチ及びその HI-TS 成分における TG 分析

バインダーピッチ及び含浸ピッチにおける溶媒溶解度

Solvent solubilitiesof impregnation and
Binder pitches

200
300
400
Temperature (℃)

TGA profiles of binder and impregnation pitches* Black line: Pristine, Red line: HI-TS fraction of IP and BP

B
P

67

Novel method for quantitation of aromaticity
HPLC analysis

Standard materials

GC-AED analysis

1 ring2ring 3 ring4 ring

Over 5 ring

Phenanthrene
NaphthaleneAnthracene
Naphthalen
e

Pyren
e

Benzene
0

2

Pyren
e
Anthacene
Perylene

Perylen
e
4

6

8

10

Retention TimeB : Benzene ( 1 ring, Retention Time : 3.18min)
N : Naphthalene ( 2 ring, Retention Time : 3.84min)
P : Phenanthrene (3 ring, Retention Time : 4.77min)
A : Anthracene ( 3 ring, Retention Time : 5.03min)
Py : Pyrene ( 4 ring, Retention Time : 5.72min)
Pe :Perylene( 5 ring, Retention Time : 7.87min)

0

100

200

300

400

500

600

700

Temperature (℃)
N : Naphthalene ( Temperature : 194.8℃)
A : Anthracene ( Temperature : 289.0℃)
Py : Pyrene ( Temperature : 329.3℃)
Pe : Perylene ( Temperature : 407.6℃)

68Analyses of CT
GC-AED analysis

HPLC analysis
B N P A Py

N APyPePe

TI-THFS
HI-TS
HI-TS

HS

HS

0
2

4

6

8

10

12

100

200

14

HS
H I-TS
TS

59
34
92

芳香族環含有量-面積比 (% )
1環
4.4
5.6
4.2

2環
1.1
3.6
2.0

3環
59
26
47

HS: almost 3 membered rings
HI-TS: over 3 membered rings

4環
20
22
21

400

500

600

700

Temterature (℃)

Retention Time (min)

溶解度 (% )

300

5環以上
18
42
27

溶解度 (% )HS
H I-TS
TI-TH FS
TS
TH FS

59
34
2.4
92
95

芳香族環含有量-面積比 (% )
1環
6.3
0.09
0.01
4.0
3.9

2環
38
2.5
3.0
25
24

3環
24
14
5.7
20
20

HS: 2 – 4 membered rings
TI-THFS: Over 4 membered rings

4環
18
30
27
22
23

5環以上
15
53
65
28
30

69

HPLC analyses of CTP

70Adjustment of molecular compositions of BP
100%

80%

PI
THFI-PS60%

TI-THFS
HI-TS

40%

バインダーピッチHS
20%

CTP294 40Torr 3H
CTP320 40Torr 3H

0%

バインダー
Fig 5.1

CTP294

CTP320

調製ピッチにおける各溶媒を用いた溶媒溶解度図(バインダーピッチ, CTP294-40Torr,CTP320-40Torr)

100
80

wt%

60

0

40

5

10
15
Retention Time (min)Fig 5.3

調製ピッチにおける HPLC 分析

バインダーピッチ
CTP294 40Torr 3H

20

CTP320 40Torr 3H

0含浸ピッチ100

バインダーピッチ

CTP294200
300
400
Temperature (℃)

500

600

Fig 5.2 調製ピッチの N2 雰囲気下における蒸留温度別 TG 分析(バインダーピッチ, CTP294-40Torr,CTP320-40Torr)(バインダーピッチ, CTP294-40Torr,CTP320-40Torr)

20

71

Mesophase pitch based highperformance carbon fiber• Heat treatment temperature: over
2200oC• Tensile Strength: over 2500MPa• Young’s Modulus: over 450GPa• Elongation: less than 0.7%
• Thermal conductivity: over 200 W/mK

Mesophase Pitch➢Intermediate to Metallurgical and Needle Cokes➢Precursor for Carbon Fiber
Molecular Recognition
Controlled Syntheses
Nanoscopic Views➢Quantitative Recognition and Identification of
Molecular Assembly➢Structural Hierarchy

Further Development : Functionality
and Applications

73

Preparation of Mesophase Pitch

MPCF Production Processes

Li-ion電池のマーケットと特性
Global market of Li-ion battery in ESS
Source : HIS iSuppli September 2011

Requirements of Li-ion battery as
power sources of ESS and EV

6 billion dollar

High
power
High
capacity

Global market of Li-ion battery in EV
Source : HIS iSuppli August 2011

Long
life
Requirementsof Li-ionbattery

10 billion dollar

Safety

Low
cost

Low
Temp.
75

Li-ion電池用負極って何?

76

Li metal anode: High reducing agent, Almost kinds of electrolyte would be reduced with Li-ion
and nucleated as dendrite metal crystal ⇒ Moli energy (Canada): NTT mobile phone (shortaccident in Tokyo), 1989
Resin derived hard carbon was first selected as a safe anode for LIB: SONY, 1991
Synthetic graphite (1989, Ashahi Kasei, Yoshida) (1993, Panasonic, C6Li, 372 mAh/g) ⇒Natural Graphite)

Safety: Li+ ⇌ Li+
C6Li: Low potential similar with Lio
Carbon material: Chemically and Physically stable, Electrically and thermally conductive

Li-ion電池用負極材の種類と負極原理?
Graphite: Mainly Li+ intercalation & deintercalation
Hard carbon: Mainly Li+ insertion & desertion (Doping & dedoping)
Soft carbon: Mixing of intercalation and doping?
Precursor

Graphite(over 2800oC)

Natural / Artificial graphite
MCMB, Needle cokes

VGCF

Soft Carbon

MCMB

Graphitizable carbon

Meso phase pitch(600~800oC)

Green cokes

Advantages

Low discharge potential (≈ 0.2V)

Long cycle life

High capacity (700~1000mAh/g)

Low cost

Hard Carbon

Thermosetting polymer

High capacity (400~700mAh/g)

Non-graphitizable

Glassy carbon, CoalHigh rate performancecarbonOrganic material

Low discharge potential (≈ 0.1V)

Stabilized isotropic pitch

Low cost(1000~1400oC)

Disadvantages

Low discharge capacity (372 mAh/g)
Poor rate performanceHigh cost

High discharge potential (≈ 1.0V)

High irreversible capacity
Poor cycle stability

Large irreversible capacity77Preparations of anodic carbons of Li-ion battery
Natural graphite

Purification

Purified pitch
High purity resin
High purity
biomass

Purified pitch

Heat treatment+ pitch & Grinding

AC coated NG+B, Graphitization

Needle coke
Regular coke
Purified pitch

Purified NG

Synthetic
Graphite

Grinding

Extraction
Heat treatment

MCMBs

Heat treatment

Heat treatment+B, Graphitization

Hard carbon

Soft carbon

Grinding & Purification

SG

Hard carbon

Grinding

Soft carbon

Price of carbon anodes: Almost no room for technical modifications!
• Natural graphite: $ 3-5/Kg, Synthetic graphite: $ 3-10/Kg• Hard carbon: $ 3-5 Kg• Soft carbon: $ 3-5 Kg• Conductive material: $ 10-20/Kg
Kyushu University UI project Kyudai Taro,2007

7
9

4. 気相炭素化:• 炭素ナノ繊維の調製

Nano-carbons
Fullerene

Zero dimension
Basal surface
Nano-size

High price
Very limited application
Mass-production(Frontier Carbon Tech.)

Graphene

Two dimension
Basal surface
Nano-size

Somewhat high priceBroad application
Mass-production

CNT

One dimension
Basal surface
Nano-size

Relatively high price
Patent problems
Mass-production(Showa Denko)
Limited application

CNF

One dimension
Various surfaces
and structures
Nano-size

Relatively low price
Patent problems
Mass-production(Mitsubishi Materials)
Limited applications
80Selective Preparation of CNFs
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,
High Graphitic CNF
High Dispersable CNF
N-doped CNF

Structural Modifications
Mesoporous CNFs
Activation

CNF functional composites
CNF-Si, SiO, TiSi
CNF-NG、CB
CNF-SiO2, CNF-MgO

Metal & Metal Oxide Nano-chain

Electric oxidation

Electro-spun CNF
Indoor polutions
Dilute NOx
De-metal, De-particulation

Fe3O4, MoO2 nanochain
SiO2, SiC nanofibers
Pt, PtRu, Pd, Au nanochain
81

Structural variety of CNFs
Typical classification of CNF Structure- graphene ((002) layers) alignment to the fiber axis, TEM observation< Simple cases of CNF structure >•However, complicated structure is often found.
•The morphological diversity confirmed simply by SEM observation cannot be neglected, considering possibly
their different physical properties.

Various cross sections of CNFs

Polygonal

CircleDifferent Surface Characteristics

Cross
82

Structural varieties of CNFs

1）Preparation of various CNFs that are best for the special applications
2）Lower price3）Proper method for the mass production
Kyushu University UI project Kyudai Taro,2007

Control of Graphitic Properties of TCNFs

MnFe37_CO14
MnFe55_CO14
MnFe73_CO14
MnFe37_CO41
MnFe55_CO41
MnFe73_CO41
Fe_CO14
Fe_CO41
NiFe462_CO14
NiFe462_CO41
NiFe642_CO14
NiFe642_CO413530

Lc(nm)

25
20
15

10
5
0
3.35

3.36

3.37

3.38

3.39

3.4

3.41

3.42

3.43

d002( Å)

84

Control of surface area

~150 nmRough surface

400

CBF

350

2

Surface Area (m /g)

300
250

50~70 nm

200
150

Metal

100
50
0
20

30

40

50

60

70

80

Fibril Aggregate

Ni Content (wt %)• CBF fibers 250 ~ 350m2/g, Metal fibers 20 ~ 200 m2/g
• CBF fibers shows 2~10 times higher SA than Metal fibers.
• SEM of CBF fibers with SA around 300 m2/g: small fibrils,
fibril aggregate, and rough surface one like activatedone.
85

Highly graphitic CNFs
◼ CNF of similar graphitic properties with Natural Graphite◼ CNT usually shows low graphitic properties◼ Conductive materials or supports for heterogeneous catalysts
GPCNF-N

PCNF, HCNF
黒鉛化

GPCNF
硝酸処理

G-PCNF-N
B黒鉛化

BA-GGPCNF-N

86

Reaction Temp.
530oC

Carbon Conversion Yield (%)

N

60
50
40
30
20
10
0

25

12

C10N
10

20

N/C

Reaction Rate
15 (Growth Rate)

8

C18N

6

C21N
10

C Conv.

4

C54N

5

2

C167N
0

Ethylene
Hydrogenml/m (g)He
Acetonitrile (liq.)
l/m
Input N/C
at.%

ET01 ACN01 ET02 ACN02 ACN03 ACN04 ACN05

160
40
0
0
0

160
40
0
35
4.6

40
40
120
0
0

40
40
120
35
14.5

0
40
160
35
50

0
40
160
70
50

0
0
200
35
50

N/C atomic ratio of CNF (%)

N-Source: Acetonitrile

Reaction Rate (g CNF/hr g cat.)

N-doped CNFs

0

Total
200
ml/m

87

Preparation of N-doped CNFs
A.

Direct Synthesis of Carbon Nanofibers with Nitrogen (the method of this study)

B.

Deposition of Nitrogen Components on Carbon Nanofibers (Post-synthesis)• Using Carbon Sources Containing Corresponding Heteroatoms• Mixing General Carbon Sources with a Nitrogen Source (NH3)
Expected features
Route A

Route B

• One step synthesis• Graphitic structure• N both in-plane and at the surface (edge)• Two step synthesis• Amorphous region at the surface(probably unstable)• N selectively at the surface (edge)

Direct Synthesis
N

N
N

N

N

N

N

N

N

N

N

N

N

N

Coating

N
N

N
N

N

Post-Doping

88

TEM & SEM of SiOx NFs• PS in Toluene* completely soluble
TEM of SiOx-NF• PS/HCNF 1/5 (w/w)
LessHerringbone
fused• 450oC in Air
textureSEM of SiOx-NF

Independent
50
nm• Herringbone-like aligned channels• Several nm-sized width89

Surfaces of PCNF
p-CNF

p-CNF-GRef.) S. Lim, et al.. J. Phys. Chem. B 108 (5), 1533 – 1536 (2004)
p-CNF-G-NA

p-CNF-G-NA-G

p-CNF

According to the graphitization degree,
we found some difference at edge plane by TEM analysis

90Various CNF composites

Magnifying the functions of basic materials：Silica,Alumina,Si,TiO2, Magnetites
91

Some problems of CNFs
1. Patents: Relatively free but some application patents
should be considered.
2. Price: ~10~200 $ /kg- Effective process for mass-production
3. Dimension & Uniformity control- Diameter- Surface control; edge / functional groups- Linearity- Crystallinity, surface area
4. Useful skills : Purification, Dispersion
Objective of this study
92Preparation (Fixed Bed Method)
Preparationof Catalyst
Bulk Catalyst

No purification
No further heat treatment

No ultra-fine particle

Gas

Furnace

CO or C2~C4 HC gas /H2

400 ~ 650 ℃
One step reaction

Furnace

Product
Clean surface
Controllable texture
Controllable graphitic property
Controllable surface area
Long or short aspect ratio
Controllable diameter
High yield

Applications

Mass flow
controller

exhaustQuartz tube
CO

H2

He
Catalyst
in the quartz boat

Temperature
controller

Catalyst : Transition metals, Their alloys or supported catalyst
Catalyst preparation method : co-precipitation
1) Best, R. J. and Russell, W. W., J. Amer. Soc. 76, 838(1954)
2) Sinfelt, J. H., Carter, J. L. , and Yates, D. J. C., J. Catal. 24, 283(1972)

Reduction : H2/He(1/9, 200sccm//4.5 cm diameter tubular furnace, 2hReaction : CO/H2 (4/1 & 1/4v/v%), 200 sccm// 4.5 cm diameter tubular furnace
Reaction Time & temperature : 1 h, 540 ～ 675 ℃
93Mass Production of CNFs
Horizon type
Capacity：several grams
Capacity：H-, P-CNF 100g/1batch
T-CNF 20g/1batch

Capacity: 500g/day

Scale upVertical type

Scale upVertical typePressure94

Discussion for growth processes
C2H2 or CO
C

1

C

2
C

Catalyst

C

Metal

C

4

C

C

Joint

C

Nano-rod

3C

1’

C atoms segregate at ●the● step edges and metal●
atoms at the step edges move toward the headof the metal, resulting in the elongation of themetal
growthlayersof graphenetheWhenandthe thegraphenegrow uplayer
to a fromcriticalth
stepedges.
ickness, a graphitic-cluster forms as a nano-rod o
Thermallyr astablishednano-plate depending
Joint on the surface state of t
he metal.
Furthermore, when the metal surface energy canno longer be compensated for by the energy gain
ed by binding the graphitic fibre to the surface, thJointe elongated metal contracts to initial shape.

Nano-plate
Kyushu University UI project Kyudai Taro,2007

95

Catalysts for CNF Preparation• Mono-metal- Fe, Co, Ni- Fe, Co, Ni / Supports• Support: Alumina, Silica >>> MgO• Bimetallic Catalyst- Fe, Co, Ni / Fe, Ni, Mn, Cu, …/Supports• Trimetallic Catalyst- Fe, Co, Ni / Fe, Ni, Cu, Mn / Cr, Al,…/Supports

Functions of Second or Third Metals ?
96

Main Catalyst

2nd Catalyst
Cr
Fe:Cr:Mg=6.4:1.6:2
収率 : 4.6倍
繊径 : 40nm
TubularMn

Fe
Fe:Mg=8:2
収率: 1.2倍

Fe:Mn:Mg=6:2:2
収率 : 1.1倍

Cu
Fe:Cu:Mg=6:2:2
収率 : 2.0倍

Ni

3rd Catalyst
Mo
Fe:Cr:Mo:Mg=6:1:1:2
収率 : 27.8倍
繊径 : 20nm
TubularCo
Fe:Mn:Co:Mg=4:2:2:2
収率 : 11.6倍
繊径 : 50nm
不均一 CNF

Co
Fe:Cu:Co:Mg=6:1:1:2
収率 : 60.2倍
繊径 : 180nm
Herringbone CNF

Co

Fe:Ni:Co:Mg=7:0.5:0.5:2
収率 : 60.2倍
繊径 : 120nm
Tubular97

Tri Metallic Catalysts

Dia
me
ter

60

37.5
45

75

)
es
(tim
lds
Yie

of
CN
F(
nm
)

0

Co:Cr:Mg=6:2:2
Co:Mn:Mg=4.8:3.2:2
Co:Al:Mg=6:2:2
Co:Fe:Cr:Mg=4:2:2:2
Co:Ni:Cr:Mg=4:3:1:2
Fe:Cr:Mg=6.4:1.6:2
Fe:Al:Mg=4:4:2
Fe:Ni:Co:Mg=7:0.5:0.5:2
Fe:Cr:Mo:Mg=5.77:1.44:0.8:2❑ 연구결과
수율, 섬경, 섬유의 구조 등에 영향을 줄 수 있는
Cr, Mn, Al 등의 새로운 보조촉매 발굴

30

112.5
15

150
450

675
600
525
o
Synthesis Temperature ( C)

1. Co 주촉매에 대한 보조촉매의 효과- Cr 보조촉매는 낮은 합성온도에서 높은 촉매수율을 보이며,합성온도가 낮아짐에 따라 Herringbone 구조의 섬유가 합성됨.
- Mn 및 Al 보조촉매는 높은 합성온도에서 높은 촉매수율을
보이며, 대부분 Tubular 구조의 섬유가 합성됨.

0 2. Fe 주촉매에 대한 보조촉매의 효과- Cr 및 Al 보조촉매 모두 합성온도가 높을수록 촉매수율이
750증가하는 경향을 보이며 Tubular 구조의 섬유가 합성됨.
- Cr 보조촉매의 경우에는 촉매수율이 매우 낮으나 반면겉보기밀도가 매우 낮은 섬유가 합성됨.
- Cr 및 Mo 보조촉매를 같이 사용할 경우에는 30배 이상의매우 높은 촉매수율을 얻을 수 있음.
3. FeNiCoMg 촉매- 최대섬경 120nm 정도의 매우 굵은 Tubular 섬유를 합성할 수있는 촉매시스템.
- Ni과 Co의 함량이 각각 0.5로 동일한 경우에 가장 높은촉매수율 및 가장 균일한 섬유를 얻을 수 있음.
98

Tri Metallic Catalysts
0.00

100

0.50

50

0.75

1. 주촉매에 대한 보조촉매의 효과- Cr 보조촉매는 낮은 합성온도에서 높은 촉매수율을 보이며,Mn 및 Al 보조촉매는 높은 합성온도에서 높은 촉매수율을 보임.
- 거의 모든 촉매조성에서 Tubular 구조의 섬유가 합성됨.

25

1.00

0

❑ 연구결과
경제적으로 저렴한 C3H8 가스를 이용하여 C2H4 가스보다 다소 높은 온도에서 CNF를 합성하였음

)
nm
F(
CN
of

Bu
lk D
en
sity

75

ter
me
Dia

0.25

Co:Fe:Cr:Mg=4:2:2:2
Co:Ni:Cr:Mg=4:3:2:1
Co:Mn:Mg=4.8:3.2:2
Fe:Al:Mg=4:4:2
Co:Al:Mg=6:2:2
Fe:Ni:Co:Mg=7:0.5:0.5:2
Fe:Ni:Mg=1:4:5
Co:Cr:Mg=6:2:2
Co:Mn:Ni:Mg=3:2:3:2

0
15

30
Yields (times)

45

60* 모든 CNF의 합성온도는 700℃임.
(Co:Ni:Cr:Mg=4:3:1:2, Fe:Ni:Mg=1:4:5 촉매는 600℃에서 합성한 결과임)2. FeNiCoMg 촉매- C2H4 가스를 이용하여 합성했을 경우와는 전혀 다른 소재가얻어짐.
- 50nm 정도의 섬유도 관찰되었으나 거의 대부분이 섬유형태가아닌 카본덩어리였으며 겉보기밀도 또한 매우 높은 편임.
3. 향후 연구 방향- 합성 후 배출되는 가스의 성분을 분석할 필요가 있음 → CH4,
C2H2, C2H4 등의 가스가 배출될 경우 이를 분리 수집하면 다른
CNF 소재의 합성에 이용가능할 것으로 예상됨.
- Ni을 주촉매로 이용할 경우 고온에서 Herringbone 구조의
CNF를 합성할 수 있을 것으로 예상됨.
- C3H8 가스를 이용한 CNF 합성에서의 반응 메커니즘 연구.

99

Standard CNFs
Sample #KNF-SPR
PlateletNano-rod

SEM

TEM

Properties
Applications
Platelet
電池材料, 触媒担
high grapht. deg.
体, 触媒担体
80 ~ 400 nm, SA 90 m2/g例) 高活性水素化
d002 3.36Å, Lc(002) 30 nm
触媒Ru/PCNF

Etc.
70 g/日KNF-SH
Herringbone

Herringbone
複合材料, ガス貯high surface area
蔵, 吸着剤,触媒担70 ~ 500 nm, SA 150 m2/g
体, FEDd002 3.45Å, Lc(002) 3 nm
例)DMFC用PtRu触媒担体

100 g/日KNF-ST
Tubular
高黒鉛化
性Tubular
複合材料, 吸着剤,
thin walls, open tips
触媒担体, 触媒
high grapht.deg.
20 ~ 50 nm, SA 90 m2/g
d002 3.37Å, Lc(002) 13 nm

20 g/日KNF-FM
Tubular
小繊径

tubular, hollow
5~15 nm, 4 -7 walls

複合材料、触媒担体、FED

20 g/日100

CNF (Small & Middle Diameters)
Sample #SEM

TEM

Properties

Applications

Product

KNF-CM
小繊径
高分散

Herringbone,hollow
7 ~ 20 nm

複合材料、吸着剤、
触媒担体、FED

20-30 g/日

KNF-CC
小繊径

Herringbone
7 ~ 15 nm

複合材料、吸着剤、
触媒担体、FED

15-20 g/日

KNF-NM
中繊径

Herringbone
10~60 nm (30~40)

複合材料、吸着剤、触媒担体

50-70 g/日

KNF-NF
中繊径
直線性

Herringbone
20 ~ 50 nm
Straightness

複合材料、吸着剤、触媒担体

50-70g/日

101Structural Units of CNFs

Kyushu University UI project Kyudai Taro,2007

STM images of MWCNTs; Nano-rod bundle type

units
and their periodicity
in carbon nanotubes,
D., An, B., Yokogawa, K.,arranged
Ling, L., Miyawaki,
J.,
STMStructural
image
shows
the presenceof theLong,
quasi-periodically
Joints.
Mochida, I., Yoon, S.-H., Small 6 (22), pp. 2526-2529 (2010).
Nano-rod bundles are observed between the joints.
Kyushu University UI project Kyudai Taro,2007

103

10
4

5. 固相炭素化• バイオマスを用いたLi-ion電池負極材の調製

Kyushu University UI project Kyudai Taro,2007

105

Hard carbon from Mangrove tree – the effect ofpreheat treatment on its electrochemical properties of
Li-ion battery✓Objective
Development of biomass derived cheap hard carbon with relative high
1st cycle CE✓ Contents▪ Investigation of preheat treatment effect on the 1st cycle
Coulombic efficiency in the preparation of hard carbon using
biomass as raw material❖ Yu-Jin Han, et al., IMPRESS, 2013, 3, 571.
“Influence of preparation conditions of biochar from raw biomass on initial Coulombic
efficiency of biomass derived hard carbon in Li-ion batteries”

From Biomass Char106

➢ Preparation of hard carbon from Mangrove char
MillingHeat treatment
Particle size lessat 1000oC
Than 45μm（Hard carbon）（Mangrove char）• Rate performance of
biomass derived hard carbon• Charge-discharge
properties

High rate
performanceHigh discharge
carpacity
Cheap hard carbon with high discharge capacity can be prepared from bio
mass through suitable selection of raw material and heat treatment.
* T. Liu, et al., Electrochimica Acta, 2010, 55, 1696.

Status and distribution of mangrove forests of the world107< C. Giri et al., Global Ecology and Biogeography 20 (2011) 154 >➢ Total area of mangrove : 137,760 km2 (2000年）• Continent : Asia (42%), Africa (20%), North and Central America (15%), Oceania (12%),South Africa (11%)• Country : Indonesia (22.6%), Australia (7.1%), Brazil (7.0%), Mexico (5.4%)➢ Price of mangrove charcoal : US dollar 0.4-0.5/kg (Deal Indonesia CV)
Price of natural graphite for battery : US dollar 0.8-2.0/ kg (Qingdao Caifeng Co. Ltd.)107

From Green Tree108

Development of cheap hard carbon➢ Investigation of structural effect of hard carbon on the electrochemical
properties.
➢ Optimization of preheat treatment condition for hard carbon preparation• Necessity of preheat treatment（2） Pretreatment（1）No preheat treatment

1st HT（800℃）

1st HT
2nd HT（800℃） （1000℃）

Preheat treatment（Hard carbon）（Mangrove
Hard wood）

2nd HT（1000℃）（hard carbon）(Mangrove
Hard wood）（char）

Preheat treatment of Mangrove tree
➢ Yield of 1st HT at 800oC

109➢ Cha-discha properties of
hard carbons

Preheat treated（500℃PHT ⇒ 1st HT of 800℃）

No PHT（only 1st HT at
800℃）

Potential/V vs. Li/Li+

1.4

1st CE：54％

1.2
1.0

1st CE：72％

0.8
0.6
0.4

T500-800-1000
T800-1000

0.2
0.0
0

100

200

300

400

500

600

Capacity (mAh/g)※ Hard carbon prepared at 1000℃ from
Mangrove tree

• Preparation yield and 1st cycle CE were improved through preheat treatment ⇒ PHT is necessaryPreparation of hard carbon and its Li-ion charge models 110
Preparation of hard carbon

Li-ion storing sites➢ Preheat treatment• Temp：450、 500、550、600oC• Time： 1～49 days
• Presuure： 0.2、 0.4、 0.7 MPa➢ Preparation of hard carbon

熱処理：1000-1200oC

Charcoal
Milling less than 45 µm

Carbonization
1st HT: 800℃、30 min、Ar
2nd HT: 1000℃、1h、Vacuum

Evaluation of electrochemical property
Charge;(CC/CV) ： 30 mA/g、0.0～1.5 V、To 3 mA/g
Discharge (CC)： 30 mA/g、0.0～1.5 V* Chul Wan Park, et al., Carbon, 2000, 38, 995.

Site I (Potential range：0.0－0.1 V)
1000‐1200oC heat treatment: Removal of heterogeneo
us atoms → formation of storing sites
Site II (Potential range：0.1－0.9 V、1.3－1.5 V)
Between graphene sheets
Site III (Potential range：0.9－1.3 V )Distortion of graphene sheet clusters

CTPコ－ティング黒鉛

Effect of pretreatment on the electrochemical properties
Charge-discharge properties

Discharge capacities•Charge-discharge: P：0.7 MPa、D：３ days
1.4

• Discharge capacity according to potential

Potential/V vs. Li/Li+

1.2

314

100

173

37

4

HC -T500

396

163

183

44

6

HC -T550

368

139

181

43

5

HC -T600

353

130

176

41

6

Region 3

P0.7-D3
HC-T450
HC-T500
HC-T550
HC-T600

0.6
0.4
0.2

Region 2

0.0

Region 1

0700•Elemental analysis

90

70
400
60

300

500
550
Temperature (°C)

600

50

Coulombic efficiency (%)

80

500

450

Atomic ratios (%)

Atomic ratios (wt%)

ChargeDischarge
C.E

600

領域 4
(1.3～
1.5 V)

100

200
300
400
500
Capacity (mAh/g)•Charge-discharge and 1st cycle CE

Capacity (mAh/g)

HC-T450

Samples

0.8

200

Total
(0.0～
1.5 V)

Discharge capacity (mAh g-1)
領域 1
領域 2
領域 3
(0.0～
(0.1～
(0.9～
0.1 V)
0.9 V)
1.3 V)

Region 4

1.0

111

SamplesC

H

N

Odiff.

Ash

H/C

O/C

HC-T450

92.25

0.25

0.60

3.75

3.15

3.25

3.05

HC -T500

93.35

0.31

0.43

4.39

1.52

3.99

3.53

HC -T550

92.50

0.25

0.23

2.95

4.07

3.24

2.39

HC -T600

93.38

0.25

0.28

2.80

3.29

3.21

2.25

Pressure effect on the electrochemical properties
Charge-discharge properties

Discharge capacities•Charge-discharge: 温度：500oC、P：圧力、D：３日間• Discharge capacity according to potential

Region 4

Total
(0.0～
1.5 V)

Discharge capacity (mAh g-1)
領域 1
領域 2
領域 3
(0.0～
(0.1～
(0.9～
0.1 V)
0.9 V)
1.3 V)

HC-P0.2

352

141

167

41

3

HC-P0.4

383

154

179

43

7

HC-P0.7

394

171

178

38

7

1.2
1.0

Samples

Region 3

0.8

T500-D3
HC-P0.2
HC-P0.4
HC-P0.7

0.6
0.4
0.2

Region 2

0.0

Region 1

0

200 300 400 500
Capacity (mAh/g)•Charge-discharge and 1st cycle CE

700

ChargeDischarge
C.E

Capacity (mAh/g)

600

80
70

400
60

300
0.2

0.3

0.4

0.5

Pressure (MPa)

0.6

0.7

•Elemental analysis

90

500

200

領域 4
(1.3～
1.5 V)

100

50

Coulombic efficiency (%)

Potential/V vs. Li/Li+

1.4

112

Atomic ratios (wt%)
SamplesAtomic ratios (%)

C

H

N

Odiff.

Ash

H/C

O/C

HC-P0.2

89.70

0.68

0.72

7.65

1.21

9.10

6.40

HC-P0.4

90.58

0.68

0.49

7.47

0.74

9.01

6.19

HC-P0.7

93.11

0.30

0.50

3.97

2.13

3.87

3.20

113

Effect of pretreatment time on the electrochemical properties
Charge-discharge properties•Charge-discharge
1.2

HC-D3

396

163

183

44

6

HC -D7

393

170

177

41

6

HC -D29

402

174

180

41

7

HC -D39

417

188

181

42

6

HC -D49

366

153

168

41

5

Region 3

1.0
0.8

P0.7-T500
HC-D3
HC-D7
HC-D29
HC-D39HC-D49

0.6
0.4
0.2

Region 2

0.0

Region 1

0

100

200
300
400
Capacity (mAh/g)

500•Charge-discharge and 1st cycle CE
700
ChargeDischarge
C.E

600

HC-D39
1st cycle CE：81％

70
400
60

300

0

5

10 15 20 25 30 35 40 45 50

Time (day)Atomic ratios (%)

Atomic ratios (wt%)
80

50

領域 4
(1.3 V-1.5 V)•Elemental analysis

90

500

200

Total
(0.0 V-1.5 V)

Discharge capacity (mAh g-1)
領域 1
領域 2
領域 3
(0.0 V(0.1 V(0.9 V-0.1 V)-0.9 V)-1.3 V)

Samples

Coulombic effiency (%)

Potential /V vs Li/Li+• Discharge capacity according to potential

P：0.7 MPa、Ｔ：500℃

Region 4

1.4

Capacity (mAh/g)

Discharge properies

SamplesC

H

N

Odiff.

Ash

H/C

O/C

HC-D3

93.35

0.42

0.51

3.34

2.34

5.40

2.68

HC-D7

92.91

0.46

0.63

2.99

3.01

5.94

2.41

HC-D29

93.30

0.20

0.44

3.53

2.53

2.57

2.84

HC-D39

93.07

0.14

0.26

2.74

3.79

1.81

2.21

HC-D49
92.90
0.10
0.39
CTPコ－ティング黒鉛

2.61

4.00

1.29

2.11

水素と酸素の含有量が減少What is the factor to determine 1st cycle CE?
➢SA and Pore size distribution of hard carbons

14
12

Va [cm3(STP) g-1]

N2 adsorption amount25

N2 BET

HC-D3
HC-D7
HC-D29
HC-D39HC-D4920
15

SA

Surface area (m2/g)

30

10

8
6
4
2
0

5

39日からは
比表面積が減少

29日までは
比表面積が増加

10

114

0

5

10 15 20 25 30 35 40 45 50
Time (day)

0
0.0
45

0.4
0.6
0.8
Relative pressure (P/P0)

1.0

39日からはウルトラミクロ孔サイズが縮小

CO2 BET (25℃)

35
Va [cm3(STP) g-1]

CO2 adsorption amount

40

0.2

30
25

HC-D3
HC-D7
HC-D29
HC-D39HC-D49

20
15
10
5
0
0.000

0.004
0.008
0.012
Relative pressure (P/P0)

UMP
distribution

UMP（Less than 0.7 nm）
0.016
0.4

HC-D3
HC-D7
HC-D29
HC-D39HC-D4929日まではウルトラミクロ孔サイズ
が拡大

0.5
0.6
Pore size (nm)0.7Structure control of hard carbon in the preparation step 115
Characteristics of hard carbon➢➢

Using nano-sized inner closed pores –not graphitizedNon-graphitic carbonSpecial properties•

Approach of this study➢ Optimization of hard carbon structure
through controlling the lowtemperature pre-carbonization
heat treatment

Discharge capacity (mAh/g)

Advantage: High cap., High rate5
• Disadvantage
R.E. Franklin, Proc. R.
Soc. Lond., 1951, 209,
: Low 1st CCE, Low density
196.
• Raw material ：Resin, coke, biomass Development of biomass derived
hard carbon:➢High rate performance of hard carbon Development of low cost hardcarbon using Mangrove based400
biomass
through
simpleheat
350
treatments
300
250
200

➢

Commercial
graphite
HC-D39150
100

10Cで2倍
以上高出
力性

50
0.1

0.5

1

2
C-rate5100.1

Price of raw materials• Price of mangrove char : US dollar 0.4-0.5/kg(Deal Indonesia CV)• Natural graphite: US dollar 0.8-2.0/kg(Qingdao Caifeng Co. Ltd.)Summary116

1st cycle CE of hard carbon derived from Mangrove tree was improved
through the optimization of preheat treatment conditions.
• Preheat treatment is closely related to the distribution of ultra
micropores which might be related to the 1st cycle CE of hard carbon.
• Preheat treatment conditions of 500oC under 0.7 Mpa for 39 days canafford the cheap hard carbon which has discharge capacity of 417 mAh
g‐1 with 80.5％ of 1st cycle CE.
⇒ Hydrogen and oxygen amounts and UMP distribution might beimportant factors to determine the electrochemical
propertiesof hard carbon.

まとめ
1．人造黒鉛材には易黒鉛化性炭素と難黒鉛化性炭素がある．
難黒鉛化性と易黒鉛化性炭素は積層単位の大きさの違いからドメインの構造が異なる．
2．炭素材は気相，液相，固相炭素化で製造される．95%以上の人造黒鉛は液相炭素化で製造される．
3．ナノ炭素中，フラーレン，CNTおよびCNFは気相炭素化で合成される．
一部易黒鉛化性炭素（VGCF, HOPG)は気相炭素化で製造される．
4．易黒鉛化性炭素材は主に液相炭素化によって製造される．
5．バイオマスおよび熱硬化性樹脂を用いた炭素材は固相炭素化で製造される．
高分子を前駆体としたPAN系炭素繊維およびナノ炭素ナノ繊維は固相炭素化で製造される．
一部高分子を原料とした高熱伝導性炭素フィルムは固相炭素化で製造される．

ピッチとは？
•

•

•
•
•

•

•

118

ピッチは，木材，石炭などの乾留の際に得られる液状タール，オイルサンドから得られるビ
チューメン，オイルシェールの乾留によって得られる油分，原油の蒸留による残渣油，石油留分のクラッキングによって生成するタールなどを熱処理，重合して得られる常温で固体状のものの総称．
工業的には石炭の乾留の際生成される石炭系ピッチ（Coal tar pitch）と石油の蒸留の残渣から製造できる石油系ピッチ（Petroleum pitch）が重要．最近は，ナフタレンなどの芳香族化合物を触媒重合した合成ピッチも製造されるようになった．
ピッチは, 化学的には無数の縮合多環芳香族化合物の混合物であり，平均分子量は300～
1000程度の範囲の混合物ある．こうしたピッチは通常は光学的に等方性である
こうした等方性ピッチを350～450℃程度の温度で熱処理すると光学的異方性組織（メソフェー
ズ）の炭素質液晶が発達
メゾフェースピッチのテキスチャーは，これを前駆体と用いて製造されるコークス等の機能性
炭素材の化学・物理的特性をほぼ決定してしまうので，メゾフェースピッチ合成の際，原料の化学構造，熱処理の際の熱分解ならびに重合挙動をよく知っておくことはきわめて重要．液晶
ピッチはネマティック液晶．
芳香族多環縮合構造のプレナー分子が積層され，メゾーゲン単位を高温熱処理過程で形成した後，こうしたメゾーゲン単位の濃度が増加することに従って球晶が生成，その後生成した球晶の合体によって100%の光学的異方性組織を持つメゾフェースピッチが形成
液晶ピッチは，石炭の熱分解課程で最初発見された際は不溶のものと認識されたが，可溶・可融性が見つけられ，高性能ピッチ系炭素繊維の前駆体として利用．

重質油又は石炭残渣を用いた炭素材の製造模式図

119