PVdF-HFP/PVP Supercapacitor - CHERIC · 2003-12-30 · 788 HWAHAK KONGHAK Vol. 41, No. 6, December, 2003, pp. 788-794 PVdF-HFP/PVP Supercapacitor † 449-728 38-2 (2003 4 7 , 2003

HWAHAK KONGHAK Vol. 41, No. 6, December, 2003, pp. 788-794

PVdF-HFP/PVP Supercapacitor

†

449-728 38-2

(2003 4 7 , 2003 9 7 )

Electrochemical Characteristics of Composite Electrodes with Polypyrrole for Supercapacitor with PVdF-HFP/PVP

Ho-Sung Oh, Kyong-Min Kim and An-Soo Kang†

Department of Chemical Engineering, Myongji University, Yongin 449-728, KoreaSan 38-2, Nam-dong, Yongin, Kyonggi 449-728, Korea(Received 7 April 2003; accepted 7 September 2003)

5-8 wt% (BP-20 YP-17) Poly (vinylidenefluoride-co-hexafluoropropylene)

(PVdF-HFP)/polyvinylpyrrolidone(PVP) n-methyl-2-pyrrolidinone(NMP) !"#.

$%& ' ·( ), *+,, AC-ESR, -./, CV impedance ) 0 1234 ) 5+!"#.

5 wt%6 +!" 7 89, :; 1<4 = >? 1234 ) @A !1

%!B CDE,F 8 wt% FG6 !A HF 4I!"#. )J, BP-20 K CDE,

F 7 wt%L 7 *+, 34.77 F/g, AC-ESR 0.65Ω, -./ 8.16 Wh/kg MN/ 1,830 W/kgO6 P2

K QR# >?!" Ragone plot PS T 7 1MU 4V W T ? XY#.

Abstract − Composite electrodes were fabricated based on activated carbons such as YP-17 and BP-20, and conducting poly-

mer of polypyrrole (pPy) prepared by chemical polymerization in our laboratory. Mixed binders of Poly (vinylidene-fluoride-

co- hexafluoropropylene) (PVdF-HFP) and polyvinylpyrrolidone (PVP) in n-methyl- 2-pyrrolidinone (NMP) were added to the

activated carbons. Electrochemical characteristics of unit cells such as charge-discharge, specific capacitance, ESR, specificenergy, cyclic voltammetry (CV) and impedance were measured. It was noted that a pPy content within 8 wt. % greatly

increased the electrochemical characteristics, mechanical strength and flexibility with the fixed 5 wt. % of mixed binder. Espe-

cially, the BP-20 electrode with 7 wt% of pPy exhibited better electrochemical characteristics than commercialized products,with 34.77 F/g of specific capacitance, 0.65Ω of AC-ESR, 8.16 Wh/kg of specific energy, and specific power of 1,830 W/kg.

Power outputs were compatible with electric vehicle applications, in due consideration of Ragone relations.

Key words: Polypyrrole, Supercapacitor, Activated Carbon, Polyvinylpyrrolidone, Poly (Vinylidene-Fluoride-Co-Hexafluoropropylene)

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HWAHAK KONGHAK Vol. 41, No. 6, December, 2003

790

s

3.

3-1. FT-IR

°±² F % 6 Q -'] BF4− aU

n <´ @@ U -' @ EBU Fig. 10 d§¨!

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Fig. 1. FT-IR spectrum of chemically synthesized polypyrrole powder.

Fig. 2. Effect of added weight percents of polypyrrole on charge/dis-charge curves of YP-17 electrode with mixed binder.

Fig. 3. Effect of added weight percents of polypyrrole on charge/dis-charge curves of BP-20 electrode with mixed binder.

Fig. 4. Effect of addition and non-addition of 7 weight percent polypyr-role on charge/discharge curves of YP-17 and BP-20 electrodewith mixed binder.

41 6 2003 12

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B ./'( d§I" ¹ D p!".

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· CD BP-20 Ê °±² ᾪ( 7 wt%

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;n 2005 V m/ EB & 35ä 2.44% /'(

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J Ë °±² ©(0 o KÇ<kó(AC-ESR, 1 kHz)

Fig. 70 d§¨!". 0n Ç´3 YP-17B BP-20 Í[TQ

-' C >´3 °±² © CQ © AC-ESR

?@ òåAT BP-20 C 7 wt%0n 0.65ΩTQ ` ò3 B

d§¨!". EB · % ./'( EB6 Ða

¯". ./'( ` CD °±² ᾪ( 7 wt% C

© ,3 C ÊC ±bU Nyquist plot EBU Fig. 8

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°±² -' ,3 Cw" ÊB £ 1; 1

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u ~v(pseudo reaction) D p!"[8, 13].

3-2-4. 0456 $756

Fig. 5. Effect of added contents and non-addition of polypyrrole on spe-cific capacitance of electrodes with mixed binder.

Fig. 6. Effect of charge/discharge curves of 200 cycles on specific capac-itance and DC-ESR of BP-20 electrode with 7 weight percent ofpolypyrrole and mixed binder.

Fig. 7. Effect of addition and non-addition of 7 weight percent polypyr-role on ESR of electrodes with mixed binder.

Fig. 8. Effect of addition and non-addition of 7 weight percent polypyr-role on Nyquist plot of electrodes with mixed binder.

HWAHAK KONGHAK Vol. 41, No. 6, December, 2003

792

°±² ª( 5, 6, 7 % 8 wt%Q Ê Ji Ë 0456

$756U Table 10 d§¨!". ./'( ` CD >

?0 © °±² ᾪ( 7 wt%Ð ã YP-17B BP-20Ê

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w] VW -H0n supercapacitor 0456 2-7 Wh/kg

à VW0n °±² ª( 7 wt%Ð ã 0456 8.16 Wh/kgTQ

0456w" 23 EBU ¸! 1,830 W/kg 23 $75

6 Conway[4] Ragone plotr0n &´r0 a ¹TQ wå

n r' #$06 @® <' D p" Í]".

3-2-5. SEM @

|«< ` CD BP-20 Ê °±² ª( 7 wt%

Ð ã ÍÐEFJ ÉFEFJ Ê :; 1,000: & SEM

Fig. 90 d§¨!". Ji] Ê :;Wi Ñ6 % ¶ ª

Ì +Ô EB ÂÂ Ê :;3 "S WiU D p

!T Ê Ñ6 CD ¶ @® ªÌâ D pê 7

D p!". tud PVdF-HFP ÍÐEFJU -' Ê(A)w" ÉF

EFJU -' Ê :;(B) :;Wi ' ÏÐ NSJ

B Ú EF7 CD PVP0 >?B °±² )* @

¼ .:;< 2, Ê V % Ñ6U ·¾ ¯T ©

] °±²0 3^< @÷U d§¨H >?B °

±² -0n synergy BU ' ÕÛ ã+0 |«<

CD¯"[8].

3-2-6. CV

Fig. 10 % 113 ÂÂ >? YP-17 % BP-200 °±² 7 wt% ©

C -6U 5, 10, 20 % 50 mV/sQ CV0n m/

Ö56U - 6Q d%H 0 & ./'( d§3 EB

". BP-20 Ê YP-17 Êw" CD ./'( d§¨

! -60 r+ ÉFEFJU -' °±² ª( 7

wt%U ©; ã '(- >´ ;< Õ CD ./

'( d§¨!". EB Ê .:;< ½ °±²0

66 Õ #$ u /'( >? .u

/'(B F<TQ Oõ H ./'( Õ¯ ã+,

ÊB 1; 1 $6 Õ¯ frD å

Ö /r rs0 F 6Å D pTôQ CV>´ (plateau)

h@ d§I" Yoon K[14] EB Ða¯ ß r# ¿s

Q /'( 2¾ d§(". tud Ü0n I¾ » ¹

3 J E = °±² |, ^~v0 u '(

Table 1. Effect of polypyrrole weight percents on energy density and power density of YP-17 and BP-20 electrodes with mixed binder

Polypyrrole[wt%]

YP-17 BP-20

Energy density [W·hr/kg] Power density [W/kg] Energy density [W·hr/kg] Power density [W/kg]

5 4.30 261 5.85 4206 5.05 313 6.53 6417 6.33 567 8.16 1,8308 5.63 396 7.49 764

Fig. 9. SEM micrograph of BP-20 electrodes with 7 weight percent poly-pyrrole with (a) PVdF-HFP binder, and (b) PVdF-HFP+PVP mixedbinder.

Fig. 10. Effect of scan rate on specific capacitance of YP-17 electrodewith 7 weight percent polypyrrole and mixed binder.

41 6 2003 12

Supercapacitor 793

ã+"[4].

CV>´0n plateau h@3 -6 5 mV/s0n BP-20 Ê

YP-17 Êw" ' OÅ] ¹ D p!". tud -6

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@ H '( d§¨ - r#¿ CV

H ¹TQ wå '( ß$ ½¾ k ¹TQ Í

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-'( >´ ·åA ã+0 1-6 YP-17B BP-20

Ê0n 5 mV/sQ d§(". ® 1-6 5 mV/s r0n

ÍÎ ¨hkó3 ' ¾ 04 k` w"

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Êw" BP-20 Ê0n $6 Õ frD

' å ./'( CD" ¹ 7 D p!". EB<TQ

Ë ¡3 5 mV/s -6Q ¯".

-6 5 mV/s C YP-17 % BP-20 Ê0n °±² ª(

6|0 o ./'( Fig. 12 % 130 d§¨!". °±² ª

( 7 wt% C ./'( ` ·2". EB 0456,

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/'(B6 Ða¯". °±² © C © ,3

C ./'( Fig. 140 d§¨!". tD0n 7 D pL j

EB Ða¯ BP-200 7 wt% °±² © C Ê

` CD¯".

3-2-7. Ê .:;<

ÉFEFJU 5 wt%Q / °±² ª(0 o BP-20 Ê

æS @÷U Fig. 150 d§ !". Fig. 15(a) micropore mesopore

æSh±(HK method)U d§3 ¹ (b) mesopore macropore

æSh±(BJH method)U d§3 ¹". ©] °±² ª

( 7 wt%Ð ã BP-20 Ê BET m/O0 .:;<3 ÍÐ

EFJÐ ã 884 m2/g, ÉFEFJÐ ã 1,632 m2/g, HK m/O0

Ï æS ½ 15.8 Å0n 5P] ¿r d§¨!". eD >

? C0n .:;<(2,015 m2/g)w" °±²B ÉFEFJU

©ªTQl Ê .:;<3 r&<TQ ¦¯". Ê .:

;< QDK, frD DK ./'(B 0456 Õ

ª 7 D p!".

5.

Coconut shell1 YP-17 % ðñD1 BP-20 rî' >?0 #

$ Ji °±²B PVdF/PVP ÉFEFJU -' Ê Ji

Ë ÍÎ J · , ./'(, ESR, .:;<, 0

Fig. 11. Effect of scan rate on specific capacitance of BP-20 electrodewith 7 weight percent polypyrrole and mixed binder.

Fig. 12. Effect of polypyrrole weight percents on specific capacitance ofYP-17 electrode with mixed binder, 5 mV/s scan rate.

Fig. 13. Effect of polypyrrole weight percents on specific capacitance ofBP-20 electrode with mixed binder, 5 mV/s scan rate.

Fig. 14. Effect of addition and non-addition of 7 weight percent poly-pyrrole on specific capacitance of electrodes with mixed binder;scan rate=5 mV/s.

HWAHAK KONGHAK Vol. 41, No. 6, December, 2003

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±² @A ©; ã |«< CD Ê Ji D

p °±² ᾪ(3 8 wt% ¨ <S¯".

(3) >? BP-200 °±² 7 wt% © Ê .:;< 1,632

m2/g, ./'( 34.77 F/g, AC-ESR 0.65Ω, 0456 8.16 Wh/kg

% $756 1,830 W/kgTQ r'|] w" CD¯

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(4) 7 wt% °±² ©¯ ã '(- >´(CV) plateau

h@, -6U .Ú ã YP-17w" BP-20 Ê0n $6

Õ frD ' å ./'( ' ¹ 7 D

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p!T, 1-6 5 mV/sQ Í !".

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Fig. 15. Pore volume distribution vs. (a) micro- and meso-pore and (b)meso- and macro-pore at various polypyrrole contents of BP-20electrodes with 5 wt% mixed binder.

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