2003/11/08 多功能碳材料研究室 1

奈米孔洞材料 微小化的反應器

國立成功大學化學工程系鄧熙聖 ( 教授 ) 、粘耀仁、戴佑理、鄭焙哲、

蔡忠憲、劉信佑、劉啟徵

Nanoporous Materials Miniaturized Reactors

National Cheng Kung University

Department of Chemical Engineering

2003/11/08 多功能碳材料研究室 2

孔洞材料分析與製備技

術

孔洞高分子薄膜電極陣列

MCM 系列孔洞氧化矽

觸媒反應之 Carbon/metal redox center

孔洞材料電化學儲能機制

孔洞結構結合 吸附能預測吸附量

Gas-carbon 反應之機制

孔洞碳材製備 > 3000 m2/g孔洞形成機制

化學鍍

成膜

感測器鎳氫電池 電極

高分子充填成膜

量化製備

交流阻抗分

析超電容電極

0 10 20 30

Z ' ()

-30

-20

-10

0

Z"

()

1/2 O2N2 H O2

e-

N

H H

HNH

H H

N

O

Oxidizing siteReducing site

H O2

Support

M T O 57M T O 34

M T O 20

M T O 12

0 50 100 150 200

E q u ilib r iu m co n cen tra tio n (m g /L )

0

50

100

150

200

250

Ad

sorp

tion

cap

acit

y (m

g/g)

0 .3 0 .4 0 .5 0 .6 0 .7 0 .8

X (n m )

0 .0

0 .2

0 .4

0 .6

0 .8

1 .0

dW/d

X (

cm /

g nm

)3

M T O 57

M T O 34

M T O 20

M T O 12

米孔洞碳

規則性奈

predict

孔徑分佈 吸附量

2003/11/08 多功能碳材料研究室 3

Application of Porous Carbon in Supercapacitors (Electrochemical Capacitors)

in N2 in H2O or CO2

mixing

ZnCl2 or H3PO4 in N2

leaching

HCl

in N2

mixingalkali

leachingHCl

a. Gasification

Raw Material char Porous Carbon

b. Chemical impregnation

Raw Material slurry Porous carbon

c. Etching

Raw Material partially etched Porous carbon

carbonization gasification (activation)

2003/11/08 多功能碳材料研究室 4

Electrochemical Capacitors Have High Power Density and Energy Capacity

R. Kötz, M. Carlen, Electrochimica Acta 45 (2000) 2483–2498

2003/11/08 多功能碳材料研究室 5

Principle of Energy Storage

Conventional capacitors

V

Q Q

Dielectric

d

A

V

QC

2003/11/08 多功能碳材料研究室 6

The larger area the electrodes can provide, the more energy can be stored.

Carbon can be made with high surface area and porosity.

C1 C2

Electrolyte

Electrode 1 Electrode 2

d = 5 – 10 Å

Double Layer Capacitor

2003/11/08 多功能碳材料研究室 7

Conventional Capacitors

Double Layer Capacitors

(small d of double Layer) + (porous electrode) Very high capacitancee.g.S.A. = 1000 m2/g for porous carbondouble-layer capacitance = 10 μF/cm2

100 F/gfor capacitors with carbon electrodes;more than 1000 times higher than conventional

capacitors.

26-2

cmVolt

Coulomb101μF/cm 1

A

C

2μF/cm 2010A

C

2003/11/08 多功能碳材料研究室 8

Principle of Operation

5 - 10 Ao

1 V

Current CollectorCurrent Collector

Electrolyte, Carbon Layer

Electrolyte, Separator

2003/11/08 多功能碳材料研究室 9

超高電容目前的應用a. 消費性電子產品的電力支援系統 (backup sourc

e) 電視機記憶保護裝置 汽車音響 鬧鐘、程序控制器 相機及攝影機 全球行動通訊系統 (global system for mobile comm

unication, GSM): 每 5 ms 有 0.5 ms 的 pulse power 。EC 可增加電池壽命。

不斷電系統 筆記型電腦、 行動電話 電動玩具、電動牙刷、電動刮鬍刀

2003/11/08 多功能碳材料研究室 10

b. 各種機械、引擎的啟動器 , 尤其寒冬下可取代電池。

c. 交通號幟的電力供應

d. 電動汽 / 機車

以上應用均是利用其瞬間高放電、快充電、可靠性高及壽命長等特點。

2003/11/08 多功能碳材料研究室 11

Template Synthesis Method - Principle and Application

2003/11/08 多功能碳材料研究室 12

Preparation of Ordered Mesoporous Carbon and Applications

Mesoporous silica, like MCM48, SBA15…, etc,has been used to synthesis ordered mesoporous carbon in recent years.

Compare with traditional active carbon, mesoporous carbon not only reserves high specific surface (ca. 1500 cm2/g), but also has uniform pore size and regular nanostructure.

It can be used as catalytic supports, electrode materials, … etc.

2003/11/08 多功能碳材料研究室 13

Synthesis

Carbonized in the

burner at 900C

under N2

Template

Carbon precursor

mixed by ultrasonic oscillator

Etch template

by 1M NaOH at 50 C

Washed with

D.I. water till

pH value under

8 and dry

Analyzed by

BET,TEM,EA

…,etc

2003/11/08 多功能碳材料研究室 14

Mechanism

carbonization

template

pore wall pore mixed with

carbon

precursor

etched by

NaOH

template/precursor composite

template/carbon composite mesoporous carbon

2003/11/08 多功能碳材料研究室 15

TEM image and SBET

SBET = 1784 cm2/g

MCM48 Mesoporous carbon

2003/11/08 多功能碳材料研究室 16

Applications

Anodic catalyst support for direct methanol fuel cell (DMFC).

Electrochemical double layer capacitor. Separation and purification technology.

2003/11/08 多功能碳材料研究室 17

Materials

(a) Track etch membranes :

(b) Porous alumina membranes

polymer

Ion beam

Porous membrane

track-etched PC membrane

Anodic Alumina Oxide membrane

Pore diameter = 0.2 m

Pore diameter = 5 nm

2003/11/08 多功能碳材料研究室 18

(a) cross-section of raw membrane

(b) Sn2+ coated template membrane

(c) electroless deposition of Ni-P

(d) dissolution of the template membrane.

Experimental

2003/11/08 多功能碳材料研究室 19

Characterization of As-deposited Ni-P Films -1

SEM images of Ni-P electrode arrays

pore internal external tubule area

diameter diameter diameter length increase

(μm) (μm) (μm) (μm)

0.2 0.18 0.22 2.0 8.8 times

2003/11/08 多功能碳材料研究室 20

Ni(OH)2 + OH- -> NiOOH + H2O + e-

NiOOH + H2O + e- -> Ni(OH)2 + OH-

Characterization of As-deposited Ni-P Films -2

-0 .8 -0 .4 0 0 .4 0 .8V o lta g e (V )

-2

0

2

Cu

rren

t (m

A)

-0 .2

-0 .1

0

0 .1

0 .2 P E

N P E A

2003/11/08 多功能碳材料研究室 21

Preparation of Nanotube-shaped TiO2 and Applications

Since the discovery of carbon nanotubes in 1991 by Iijima, much research has been conducted on nanoscale tubular materials with novel properties

TiO2 is wide application in pigments, catalyst supports, fillers, coating, photoconductors, dielectric materials and so on.

TiO2 has good characteristics of chemical stability, endurance, thin film transparency and lower production costs.

2003/11/08 多功能碳材料研究室 22

Hydrothermal Method

TiO2 powders

NaOH(aq)

Heat in autoclave

Wash with HCl(aq) and D.I. water

ultrasonic

Filtering and DryingAnalysis with XRD、TEM、 BET…etc.

2003/11/08 多功能碳材料研究室 23

TEM Images

2003/11/08 多功能碳材料研究室 24

Nitrogen Adsorption

0 0 .2 0 .4 0 .6 0 .8 1R ela tiv e p ressu re (P /P o )

0

2 0 0

4 0 0

6 0 0

8 0 0

1 0 0 0

Vol

um

e A

dso

rbed

cm

3 /g

ST

P

SBET (m2/g) Vp (cm3/g)

370 1.188

2003/11/08 多功能碳材料研究室 25

Mechanism

1. Raw material treates with NaOH(aq), some of the Ti-O-Ti bonds are broken, and Ti-O-Na and Ti-OH bonds are formed.

2. Treated with HCl (aq) and distilled water, the Ti-O-Na and Ti-OH bonds react with acid and water to form new Ti-O-Ti bonds.

3. More HCl(aq) treatment

2003/11/08 多功能碳材料研究室 26

Applications

Large surface area offer a highly active photo-catalytic material for many applications. High efficient dye-sensitized solar cell. Provide a functional catalyst for chemical reaction, and

an adsorbents for chemicals. Environmental purification. Generation of hydrogen gas.