haiyang-2015 symposium poster (9 22 modified)-final

1
High-Surface-Area Graphitized Carbon Derived from Polymers for Supercapacitor Applications Haiyang Sheng, Yiran Chen, Hanguang Zhang, and Gang Wu Department of Chemical and Biological Engineering, University at Buffalo, SUNY, Buffalo, New York 14260 Introduction With a fast-growing market for portable electronic devices and the development of hybrid electric vehicles, there has been an ever increasing and urgent demand for environmentally friendly high-power energy resources. Supercapacitors, also known as electrochemical capacith ors or ultracapacitors, have attracted much attention because of their pulse power supply, long cycle life (100,000 cycles), simple principle, and high dynamic of charge propagation. + + + - - - - - Synthesis & Characterization NH 2 + - O S O O O O S O - O O NH 4 + NH 4 + + Fe Cl Cl Cl evaporate solvent heat treatment Chemical Activition stirring high & heating temperature NaOH or KOH Here we developed a scalable synthesis of nitrogen-doped 3D porous graphitic carbons with high-surface-area, via a graphitization process of heteroatom polymers such as polyaniline (PANI). This route offers control of the graphene morphology and doped nitrogen functionalities. Further chemical activation was also applied for those as prepared materials with enhanced capacitance reaching 300 F/g. Electrochemical Studies 0.0 0.2 0.4 0.6 0.8 1.0 -8 -6 -4 -2 0 2 4 Specific Current (A/g) Potential vs RHE (V) PANI-Fe-C-850 PANI-Fe-C-900 PANI-Fe-C-950 PANI-Fe-C-1000 PANI-Fe-C-1050 0.5M H 2 SO 4 , N 2 , 25 o C Rotating Speed: 200rpm. 0.0 0.2 0.4 0.6 0.8 1.0 -8 -6 -4 -2 0 2 4 6 8 PANI-Fe-C-900 PANI-Fe-C-900-Activated Specific Current (A/g) Potential vs RHE (V) 0.5M H 2 SO 4 , N 2 , 25 C Rotation Speed: 200rpm. 0.0 0.2 0.4 0.6 0.8 1.0 -6 -4 -2 0 2 4 6 PANI-Fe-C-900 PANI-Fe-C-900-Activated Specific Current (A/g) Potential vs RHE (V) 0.1M NaOH, N 2 , 25 C Rotating Speed: 200rpm. 850 900 950 1000 1050 40 80 120 160 200 240 280 PANI-Fe-C Specific Capacitance (C/g) Temperature of 2nd Heattreatment (C) PANI-Fe-C-Activated 200 400 600 800 1000 1200 1400 Accessible Surface Area (m 2 /g) Calculation of Capacitance Q It I t I C mV V m m V mk 0 50 100 150 200 250 300 0.0 0.2 0.4 0.6 0.8 1.0 Potential (V) Time (s) 0.5 A/g 1 A/g Summary Acknowledgement 0 1000 2000 3000 4000 5000 50 52 54 56 58 60 Coin cell with 0.9mg electrode materials. Specific Capacity (F/g) Cycle Number Coin cell with 1.9mg electrode materials. Electrode materials on carbon cloth Stainless steel Coin cell bottom Separator Coin cell cap Assembled coin cell 0.0 0.2 0.4 0.6 0.8 1.0 -2.5 -2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 Specific Current (A/g) Potential vs RHE (V) PANI-Fe(10g)-C(BP) PANI-Fe(10g)-C(KJ) PANI-Fe(15g)-C(BP) 0.5M H 2 SO 4 , N 2 , 25 C Rotating Speed: 200rpm. Synthesis & Characterization (Cont.) Electrochemical Studies (Cont.) A porous 3D graphitic carbon materials with controllable pore size and surface area was synthesized. The synthesis combined a high temperature treatment followed by a alkaline leaching treatment. The novel carbon materials was further studied as an electrode in supercapacitor, demonstrating a high capacity of 300 F/g. We thank the financial supports from the start-up fund from the University at Buffalo along with SUNY Network of Excellence in Materials and Advanced Manufacturing. Schematic representation of an EDLC based on porous electrode materials. Aniline is polymerized in the presense of ferric chloride (FeCl 3 ) by using ammonium peroxydisulfate (APS) as an oxidant, followed by solvent-evaporating, high temperature treatment, and an additional chemical activation. 0.0 0.2 0.4 0.6 0.8 1.0 200 300 400 500 600 870.88 m 2 /g Volume Adsorbed (cm 3 /g) Relative Pressure (P/P 0 ) PANI-Fe-C PANI-Fe-C-Activated 1259.71 m 2 /g Materials Specific surface area /m 2 g -1 Specific capacitance in aqueous electrolyte /F g -1 /F g -3 Commercial activated carbons (ACs) 1000-3500 <200 <80 Particulate carbon from SiC/TiC 1000-2000 170-220 <120 Carbon nanotube (CNT) 120-500 50-100 <60 Carbon aerogels 400-1000 100-125 <80 PANI-Fe-C (this work) 800-1700 200-300 230-343 Scanning electron microscope (SEM) of PANI-Fe-C (left) and PANI-Fe-C-Activated (right). N 2 adsorption isotherms of PANI- Fe-C and PANI-Fe-C-Activated. BET area and supercapacitor capacitance of carbon materials. Cycle Voltammetry of PANI-Fe- C with various Fe content. Cycle Voltammetry of PANI-Fe-C with various heating temperatures. Capacitance and electrochemical accessible surface area of PANI-Fe-C with various heating temperatures. Cycle voltammetry of PANI-Fe-C-900 and PANI-Fe-C-900-Activated in 0.1 M NaOH and 0.5 M H 2 SO 4 . Schematic representation of supercapacitor coin cell fabarication. Stability and galvanostatic charge-discharge test using coin cells with PANI-Fe-C electrodes 1 μ m 1 μ m + + + + + - - - - - + - ve ions + ve ions Separator Electrolyte Current Collector Porous Materials + + + + - - - - - - -

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Page 1: Haiyang-2015 Symposium Poster (9 22 modified)-Final

www.buffalo.edu

High-Surface-Area Graphitized Carbon Derived from Polymers for

Supercapacitor Applications

Haiyang Sheng, Yiran Chen, Hanguang Zhang, and Gang Wu

Department of Chemical and Biological Engineering, University at Buffalo, SUNY, Buffalo, New York 14260

Introduction

With a fast-growing market for portable electronic devices and

the development of hybrid electric vehicles, there has been an

ever increasing and urgent demand for environmentally friendly

high-power energy resources. Supercapacitors, also known as

electrochemical capacith ors or ultracapacitors, have attracted

much attention because of their pulse power supply, long cycle

life (100,000 cycles), simple principle, and high dynamic of

charge propagation.

++ +

--

-

-

--

Synthesis & Characterization

NH2

+

-OS

O

OO O

SO-

O

O

NH4+

NH4+ + Fe

Cl

Cl Cl

evaporate solvent

heat treatment

Chemical Activition

stirring high

& heating temperature

NaOH

or KOH

Here we developed a scalable synthesis of nitrogen-doped 3D

porous graphitic carbons with high-surface-area, via a

graphitization process of heteroatom polymers such as

polyaniline (PANI). This route offers control of the graphene

morphology and doped nitrogen functionalities. Further chemical

activation was also applied for those as prepared materials with

enhanced capacitance reaching 300 F/g.

Electrochemical Studies

0.0 0.2 0.4 0.6 0.8 1.0-8

-6

-4

-2

0

2

4

Sp

ec

ific

Cu

rre

nt

(A/g

)

Potential vs RHE (V)

PANI-Fe-C-850 PANI-Fe-C-900 PANI-Fe-C-950

PANI-Fe-C-1000 PANI-Fe-C-1050

0.5M H2SO4, N2, 25 o

C

Rotating Speed: 200rpm.

0.0 0.2 0.4 0.6 0.8 1.0

-8

-6

-4

-2

0

2

4

6

8 PANI-Fe-C-900

PANI-Fe-C-900-Activated

Sp

ec

ific

Cu

rren

t (A

/g)

Potential vs RHE (V)

0.5M H2SO4, N2, 25 C

Rotation Speed: 200rpm.

0.0 0.2 0.4 0.6 0.8 1.0

-6

-4

-2

0

2

4

6 PANI-Fe-C-900

PANI-Fe-C-900-Activated

Sp

ec

ific

Cu

rre

nt

(A/g

)

Potential vs RHE (V)

0.1M NaOH, N2, 25 C

Rotating Speed: 200rpm.

850 900 950 1000 1050

40

80

120

160

200

240

280

PANI-Fe-C

Sp

ec

ific

Ca

pa

cit

an

ce

(C

/g)

Temperature of 2nd Heattreatment (C)

PANI-Fe-C-Activated

200

400

600

800

1000

1200

1400

Ac

ce

ss

ible

Su

rfa

ce

Are

a (

m2/g

)

Calculation of Capacitance Q I t I t I

Cm V V m m V m k

0 50 100 150 200 250 300

0.0

0.2

0.4

0.6

0.8

1.0

Po

ten

tial

(V)

Time (s)

0.5 A/g 1 A/g

Summary

Acknowledgement

0 1000 2000 3000 4000 500050

52

54

56

58

60

Coin cell with 0.9mg electrode materials.

Sp

ec

ific

Ca

pa

cit

y (

F/g

)

Cycle Number

Coin cell with 1.9mg electrode materials.

Electrode materials

on carbon cloth

Stainless steel

Coin cell

bottom Separator Coin cell

cap

Assembled

coin cell

0.0 0.2 0.4 0.6 0.8 1.0-2.5

-2.0

-1.5

-1.0

-0.5

0.0

0.5

1.0

1.5

Sp

ecif

ic C

urr

en

t (A

/g)

Potential vs RHE (V)

PANI-Fe(10g)-C(BP) PANI-Fe(10g)-C(KJ)

PANI-Fe(15g)-C(BP)

0.5M H2SO4, N2, 25 C

Rotating Speed: 200rpm.

Synthesis & Characterization (Cont.) Electrochemical Studies (Cont.)

A porous 3D graphitic carbon materials with controllable pore sizeand surface area was synthesized. The synthesis combined a hightemperature treatment followed by a alkaline leaching treatment.The novel carbon materials was further studied as an electrode insupercapacitor, demonstrating a high capacity of 300 F/g.

We thank the financial supports from the start-up fund from the

University at Buffalo along with SUNY Network of Excellence in

Materials and Advanced Manufacturing.

Schematic representation of an EDLC based on porous

electrode materials.

Aniline is polymerized in the presense of ferric chloride (FeCl3)

by using ammonium peroxydisulfate (APS) as an oxidant,

followed by solvent-evaporating, high temperature treatment,

and an additional chemical activation.

0.0 0.2 0.4 0.6 0.8 1.0

200

300

400

500

600

870.88 m2/g

Vo

lum

e A

ds

orb

ed

(cm

3/g

)Relative Pressure (P/P0)

PANI-Fe-C

PANI-Fe-C-Activated

1259.71 m2/g

MaterialsSpecific surface area

/m2 g-1

Specific capacitance

in aqueous electrolyte

/F g-1 /F g-3

Commercial

activated carbons

(ACs)

1000-3500 <200 <80

Particulate

carbon from

SiC/TiC

1000-2000 170-220 <120

Carbon nanotube

(CNT)120-500 50-100 <60

Carbon aerogels 400-1000 100-125 <80

PANI-Fe-C

(this work)800-1700 200-300 230-343

Scanning electron microscope (SEM) of PANI-Fe-C (left) and

PANI-Fe-C-Activated (right).

N2 adsorption isotherms of PANI-

Fe-C and PANI-Fe-C-Activated.

BET area and supercapacitor

capacitance of carbon materials.

Cycle Voltammetry of PANI-Fe-

C with various Fe content.

Cycle Voltammetry of PANI-Fe-C with

various heating temperatures.

Capacitance and electrochemical

accessible surface area of PANI-Fe-C

with various heating temperatures.

Cycle voltammetry of PANI-Fe-C-900 and PANI-Fe-C-900-Activated in

0.1 M NaOH and 0.5 M H2SO4.

Schematic representation of supercapacitor coin cell fabarication.

Stability and galvanostatic charge-discharge test using coin cells

with PANI-Fe-C electrodes

1 µ m 1 µ m

+

+

+

+

+

-

-

-

-

-

+

- ve ions

+ ve ions

Separator

Electrolyte

Current Collector

Porous Materials

++ + +

- -- -- -

-