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1、第 1 9卷 2 0 0 4 第 1 3月 新型炭材料 NEW CARBON MATERI AI S、(J I 1 9 No 1 Ma r2 00 4 Ar t i c l e I I)：1 0 0 7 8 8 2 7(2 0 0 4)01 一 O 0 l l 一 0 5 Ne w me s o p o r o u s c a r b o n s p r e p a r e d b y a s i mu l t a n e o u s s y n t h e t i c t e mp l a t e c a r b o n i z a t i o n me t h o d f o r e l
2、e c t r i c d o ub l e l a y e r c a p a c i t o r s HOU Zh a o h u i，LI Xi n h a i，LI U En h u i，HE Z e q i a n g，DENG Li n g f e n g (C o l l e g e o fMe ta l l u r g b e o l S c i e n c eE n g in e e r i n g，C e n t r o l S o u t h U n i v e r s i t)，C h a ngs h a 4 1 0 0 8 3 C h i n a)Ab s t r a
3、 c t：A s imu l t a n e o u s s y n t h e ti c t e mp l a t e c a r b o n i z a t i o n me t h o d(S S T CM)，wh e r e tet r a e t h o x y s i l a n e(T E OS)wa s u s e d as t h e s ou r c e o f the s i l i c a temp l a te a nd r e sor c i n o l f o r ma l d e h y d e g e l as the c a r b o n p r e c
4、u r s or，was s u g g e s te d f o r t h e p r e p a r a t i o n o f me sop o r ou s c a r b o n s wi th a c o n t r ol l a b l e p o r e s l-t l c t ureA p r e c u r s o r sol u t i o n o f the s i l i c a temp l a t e p r e p a r e d b y p r e h y d r ol y s i s o f TEOS i n a l l a c i dme di u m
5、was bl e n de dwi th r e sor c i no l f o r malde h y d e s o l u t i o nTh et wosol 一 2 e l r e a c t i o n s p r o c e e d e d s im ult a n e o us l y u n d e r b a s i c c o n d i tio n s i n a s e a l e d v e s s e l a n d r e s ult e d i n the f o r ma ti o n o f o r g a n i c i n o r g a n i c
6、 h y b r i d sA n e w me s o p o r o us S S T C M c a r b o n w as o b t a i n ed by d i s so l v i n g th e s i l i c a te mp l a t e w i th 肝 i n th e h y b ri d a f t e r c a r b o n i z a t i o n，f o ll o w ed b y d r y i n g a d s o r p ti o n i s o t h e r ms a t一 1 9 6 s u gg e s t e d tha t
7、the s i l i c a t e mp l a te s y n the s i z e d s im u l t a n eo u s l y wi th the c a r b o n p r e c u r s o r p o l y me r r e s u l t e d i n the c o n tr o ll a b l e me sop o r o u s s t r u c tu r e o f t h e res ult a n t c a r b o n s C y c l i c v o l t a mme t r y me a s u r e me n t s
8、 s h o w t h a t t h e a s-p r e p a r e d S S T C M c a r b o n s e x h i b i t a h i g h ma s s-s p e c i fi c c a p a c i t a n c e u p t o 2 7 0F gTh e i r t y p i c a l me s o p o r o u s S ll a l c t u r e ma k e s t h e s e c a r b o n s p r o mi s i n g ma teria l s f o r e l ect r i c d ou
9、bl e l a y e r c a pa c i t o r s Ke y wo r ds：Me s o p o r o u s c a r b o n；So l-g e l rea c t i o n；S i mult a n eo usl y s y n the t i c t e mpl a te c a r b o n i z a t i o n me tho d；El ect r i c d ou bl e l a y e r c a pac i t o r s C L C n u mb e r：T Q l 2 7 1 T M 2 4 2 1)o m e n t c o d e：A
10、 1 I n t r o d u c t i o n E l e c t r i c d o u b l e 1 a y e r c a p a c i t o r(目)L C)(a l s o n a me d e l e c t r o c h e mi c a l c a p a c i t o r，s u p e r c a p a c i t o r)h a s r e c e n t l y r ec e i v ed c o n s i d e r a bl e a t t e n t i o n as a n i n t e r med i a t e p owe r s o
11、u r c e 。E】D lI C u t i l i z e s t h e d o u b l e 1 a y e r f o r med a t e l ect r o d e e l ect r o l y t e i n t e r f a c e wh e re e l ec t r i c c h a r g e s are a c c u mu l a t ed o n the e l ec tro d e s u r f a c e an d i o n s o f o p p o s i t e c h arg e a r e a r r a n g ed i n the
12、e l ec t r o l y t e s i d eMe s o p o r o u s c a r b on s p res e n t d i s t i n c t a d v an t a g e s as E】D LC e l ec t r od e s c o mp a r e d wi th mi c r o p o r o us c a r b o n s，e s p e c i a l l y f 0 r the o r g a n i c e l ect r o l yte目)L Cs A n o n g o i n g re s e a r c h a b o u t
13、 me s opo r o u s c a r b o n s h as b e e n c o n d u c t ed for mo re than t wo d ec ad e s M a n y n o v e l me thod s，s u c h as c a t a l yti c a c t i v a t i o n l 7 8 J，c a r bo n i z a t i o n o f p o l y me r b l e n d an d o r g a n i c g e l I an d t e mp l ate c a r b o n i z a t i o n
14、4 _ j h a v e b e e n p r o p o s ed t o p r e p a r e me s o po r o u s c arb o n s an d c o n t r o l the i r p o re s t r u c t u re A c o n v e n tio n al t e mp l a t e c a r b o n i z a tio n me t h od i s d e s c ri b e d as f o l l o ws：(1)i n t r o d u c e an o r g a n i c c o m po u n d i
15、n t o the n a n o s p a c e o f a t e mp l a t e i n o r g an i c ma t r i x e i the r b y i mp reg n a t i o n o f po l y me r s o l ut i o n，CVD o r s y n the s i s me th ods，(2)c a r b o niz e th e o r g a n i c i n o r g a n i c c o mpos i t e and(3)l i b e r a t e the res u l t i n g c a r b o
16、n f r o m the t e mp l a t eI n o r g a ni c h o s t ma t ri xe s wh i c h c an b e u s ed as t e mp l a t e s i n c l u d e l a y e r e d ma t e rials z e o l i t e s 一 po r o us s i l i c as 1 7 J，an d a n o d i c alu mi n u m o x i d e s l 1 8 j，e t c S u c h s p a t i al r e g u l a tio n o f th
17、e c a r b o nizat i o n p r o c e s s b y the n an o s p a c e ma ke s i t po s s i b l e t o c o n t r o l the s t r uc t u r e o f c arbo n ma t e rals a t n an o me t e r 1 e v e 1 b y c h angi n g e i the r the s i ze o r t h e s h a p e o f n an o s p a c eHo we v e r，the s t r u c t ur e o f t
18、he o b t a i n ed c a r b o n s i s u n d o u b t ed l y g o v e med b y the p r o pe ai e s o f the i n o r g a n i c ma t r i x 一。F o r e x am p l e th e c a r b o n res u l t i n g f r o m p o l y(f u r f u r y l al c o h o 1)(P F A)p y r o l y s i s be tw e e n the l am e l l a e o f t h e c l a
19、 y s 一i s q u i t e d i ffe r e n t f r o m tha t res u l t i n g f r o m the p y r o l y s i s o f t h i s s am e p rec u r s o r i n z e o l i t e or i n the u n i form an d s t r a i g h t c h a n n e l s o f an a n od i c a l u mi n u m o x i d e s me thod l e a v e s n o o p t i o n s t o c o n
20、 t r o l the p r o d u c t s po re s t r u c t u r e fo r the u n c h an g e a b l e f a b ric o f the t e mp l a t e s u b s t a n c eW e ma y c al1 the c o n v e n t i o n al t e mp l a t e c a r b o n i zat i o n me thod as“i n h e ren t t e mp l a t e c a r b o niz ati o n me th od”I t i s we l
21、l k n o wn t ha t the s o 1 g e 1 p r o c e s s i s a u s e f ul t ec h n i q u e t o p rep a r e n a n o c o mpo s i t e s o f o r g a n i c an d in o r g an i c ma t e ra l s wi th p r ec i sel y c o n t r o l l a b l e s t r u c t u r eI f t wo s o 1 g e l r e a c t i o ns o n e o f whic h i s th
22、e s y n the s i s o f t e mp l a t e ma t e ri al，the o the r the s y n the s i s o f the c a r b o n p r ec u rso r po l ym e r，c o u l d o c c u r s i mu l t a n e o u s l y in a r e a c t o r。the t e x ture c h a r a c t e ris ti c s o f bo th t e mp l a t e an d the Re c e i v e d d a t e：2 0 0
23、3 1 0 0 9：Re r i s e d da te：2 0 0 3 1 1 0 6 Co r r e s p o n d i n g a u t h o r：LI Xi n h a i，T e l：+8 6 7 3l _ 8 8 3 6 6 3 3，E ma i l：x h l i ma i l c s u e d u c a A u t h o r i n t r o d u c t i o n：H Ou 7 3 a a o-h u i(1 9 7 4 一)，ma l e，P h DS t u d e n t，e n g a g e d ma i n ly i n r e s e a
24、r c h o f m a te ri a l s o f e l e c t r i c d o u b l e l a y e r c a p a c i mr E-ma i l：z t nh 9 6 1 6 3 c o m 维普资讯 http:/ 1 2 新型炭材料 第 1 9卷 c a r b o n p r e c u r s o r c o u l d t h e n b e c o nt r o l l e d s y n c h r on o u s l y b y mo di f yi n g t h e s o1 g e l r e a c t i o n c o n d
25、i t i o n s Af t e r the t e mp l a t e f r a me wo r k i s r e mo v ed f r o m the c o mp o s i t e a c arbo n r e fle ct s t h e t e mp l a t e fra me wo r k c a n be o b t a i n ed Th e s i mu l t a n e o u s s o 1 g e l p r o c e s s c o mp a r e d wi t h the “i n h e r e n t t e mp l a t e c a
26、r b o n i z a t i o n me tho d”ma k e s i t po s s i b l e t o o b tai n mo r e t u n a b l e po r e s t ruc t ur e o f r e s u l t a n t c a r b o n s W e ma y c all thi s me tho d a s“s i m u l t a n e o u s l y s y n t h e t i c al t e mp l a t e c a r b o n i z a t i o n me tho d”(S S 1 M)Ka wa
27、s h i ma a n d h i s c o wo r k e rs，u s i n g t h i s me t h o d，o r e p ared me s o po ro u s c a r b o n s f r o m PF s o 1 g e l s i l i c a h y b r i d s b y the s im u l t a n e ou s f o r ma t i o n o fa c ro s s l i n k ed P FA an d t h e s i l i c a p h a s e d u rin g the s o 1 g e l p r o
28、c e s s T e t r a e t h o x y s i l ane(T E OS)was o f t e n u s ed as a s i l i c a p r ec u rso r f o r the p r o d u c t i o n o f n an o c o mpo s i t e s b y the s o 1 g e l p r oc e s s Th e s h a p e an d s i z e o f s i l i c a o b t a i n ed c o u l d be tun ed b y the s o 1 g e l r e a c t
29、 i o n c o n d i t i o n s。I n v e s t i g a t i o n i n t o r e s o r c i n o 1 f o r ma l d e h y d e(R F)g e l s and i t s c a r b o ni z e d p r o d u c t s i n d i c a t ed tha t the i r p a r t i c l e s i z e an d po r e s t r u c t ur e s h o wed s h a r p l y d i ffe ren t c h a r a c t e r
30、 i s t i c s u n d e r d i fie ren t p r oc e s s i n g c o n d i t i o n s “。T he p r e p a r a t i o n o f me s o p o r o us c arbo n s wi th a c o mb i n a t i o n o f the a bo v e t wo s o 1 g e l rea c t i o n s b y s im u l t a n e o u s l y s y n the t i c t e mp l a t e c arbo n i z a t i o
31、n me tho d was s u c c e s s f u l l y rea l i z ed i n the p r e s e n t wo r kIn a d d i t i o nthe pe rfo r ma n c e o f the r e s u l t i n g c a r b o n s as e l ec t r o d e ma t e r i a l s for EDLC was e x a mi n ed b y c y c l i c v o l t a mme t r y 2 Ex p e r i me n t a l 2 1 Pr e p a r a
32、 t i o n o f c ar b o n s Th e p r o c ed u r e o f p r e p a r i n g c a r b o n s i n t h i s wo r k i s as f o l l o ws (1)the h o mo g e n e o u s mi x t u r e o f T E 0S，e thy l alc o h o 1 d e i o ni z e d wa t e r an d HCl we r e a d d e d t o a s e a l ed r e a c t i o n v e s s e l and c u
33、r e d a t 6 5 i n a wa t e r b a th f o r s e v e r al h o u rs t o o bt ain p r ecu rso r s o l o f s i l i c a t e m p l a t e：(2)the as p r e p ared s o l was all o wed t o c o o lin an i c e b a th：(3)r e s o r c i n o l(R)and f o rm al d e h y d e(F)we re di r ec t l y s o l v ed i n d e i o ni
34、 z e d wa t e r wi th a fix ed mo l ar r a t i o o f l：2：(4)the R F s o l u t i o n was a d d ed t o the s i l i c a s o 1 whil e s n r r i n g a n d t h e j n i t i al p H o f the mi x tur e was a d j u s t ed t o 7 5 wi th d i l u t e a mmo ma；(5)the mi x ture was r e mo v ed i n t o a s e aled bo
35、 t t l e an d c u r e d for 7 d a y s a t 8 5i n a wa t e r b a th t o o b t ain mi x i n g a q u a g e l s Du ri n g thi s t r e a t me n t bo th the g e l ati o n o f 巨 oS an d the p o l y-c o n d e n s a t i o n o f R F t o o k p l a c e；(6)a f t e r c u ri n g，the g e l wa s r e mo v ed f r o m
36、the s e aled bo t t l e an d d r i ed i n air a t 8 0 c【二Th e n，the mi X i n g x e r o g e l was fur t h e r h e a t-t r e a t ed a t 1 0 0 0 c【二 for 2h u n d e r nit rog e n a tm o s p h e r e t o c a r b o n-i z e t h e po l y me r i n the mi x t u r e：(7)t h e res u l t ant c arbon s i l i c a c
37、o mpo s i t e wa s wash ed wi t h HF t o e x t r a c t c arbo n f r o m the s i l i c a f r a me w o r k and fi n a l l y(8)S S 1 M c ar-bo n was o b t a i n e d b y tho r o u g h l y washin g wi t h d e i o n i z e d wa t e r an d d r y i n gTo p r i m a r i l y i n v e s t i g a t e the e ffect o
38、f the s i l i c a f r a me wo r k o n the s t r uc t u r e of the c arbo n s，the mo l e r a t i o o f T E OS t o res o r c i n o l(S i R rat i o h e rea f t e r)v a r i ed fro m 0 t o 3 an d the 1 1 三 0S mi x t u r e s we r e t r e a t ed a t 6 5 c【二 be f o r e mi x ing wi th RF s o l u t i o n s fo
39、r d i f f e ren t t im e，s u c h as 3，6，9 h，t o o b t ain d i ffe r e n t p r e c u r s o r s o l s o f s i l i c a t e mp l a t e 2 2 Ch ar a c t e r i z a t i o n o f c a r b o n s Ni t r o g e n a d s o r p t i o n de s o rpt i o n i s o the r ms o f the c ar bo n s we re me asu r e d u s i n g N
40、o 1 0 0 0 Ga s So rpt i o n an al y z e r(Q u anta c hro me C o r p )a t一1 9 6 a f t e r d e g as-s i n g the c arbo n s p e cim e n a t 1 2 0 c【二f o r 7 hBET s u r f a c e a r e a s(S B E l )we r e d e t e r mi n ed o v e r a rel ati v e p res s u r e r a n g e o f 0 0 5 0 2 4Th e am o un t o f N2
41、a d s o r t l a t rel a t i v e p res s u re o f0 9 8 was e mp l o y ed t o d e t e r mi ne the t o t a l p o r e v o l u me Th e t-p l o t me tho d was a p p l i ed t o c al-c u l a t e the mi c r o pore v o l u me(u I1 1i)Th e n，the me s o-por e v o l u me(u )was c al c u l a t ed f r o m the d i
42、ff e ren c e be tw e e n the t o t a l po re v o l ume an d the mi c ropo re v o 1 u me In a d d i t i o nthe d e s o r 0 t i o n b r a n c h o f i s o the rm was u s ed t o d e t e r mi n e the a v e rag e pore d i am e t e r(d)wi th BJ H me tho d Th e c y c l i c v o l t a mme t r y was e mpl o y
43、ed t o c h a r a c t e r i ze the e l e c t r oc h e mi c al be h a vi o r o f the S S TC】c a r b o n s EDL e l ec tro de was c o mpo s e d o f 9 0加 S S TC】c ar bon5加 c arbon b l a c k and 5加 po l y(t e t r a fl u o r o e thy l e n e)(P r F E)E a c h c a r b o n e l ect r o d e l o a d ed a b o u t
44、3 0mg o fS S TC】c a r b o nA s an d wi c h t y p e c e l l was p re p ared wi th tw o i d e n t i c al c a r b o n e l ect r o d e s wi th a g l ass fibe r c l o th u s ed a s the s e p a r a t o r Th e e l ect r o l y t e u s e d i n e l ectroc h e mi c a l me asu r e me n t was a 3 0 加 H2 S 04 a q
45、 u e o u s s o l u t i o nCy c l i c v o l t a mme t r i c me asu reme n t s o f the c e l l s we r e ma d e i n the po t e n t i al r a n g e o f 一0 8 t o 0 8V an d the po t e n t i a l s c an rat e was fix ed a t 5 mV s 3 Re s u i t s a n d d i s c u s s i o n 3 1 P0 r e c h a r a c t e r i s t i
46、c s o f c a r b o n s Th e r e s u l t i n g S S Ta c a r b o n s e x h i b i t ed we l 1 d e v e 1 o WA me s o po r o s i t y，wh i c h was c h a r a c t e riz ed b y n i t r o g e n a d s o r p t i o n i s o the r ms a t一 1 9 6 c【二(s e e the po re s t r u c ture p ara me t e rs l i s t ed i n T a b
47、 l e 1)Th e rat i o o f S i R=0：1 d e n o t e s tha t the c a r b o n was p r o du c ed o n l y b y c a r b o n-i z i ng the RF x e r o g e l wi tho u t mi x i n g the s i l i c a t e mp l a t e F i g 1 an d 2 s h o w the n i t r o g e n a d s o rpt i o n i s o the r ms for the c a r b o n s am p l
48、e s me n t i o n ed in Ta b l e 1 Ac c o r d i n g t o the AC c l ass i fic ati o n s ，the a d s o rpt i o n i s o the r ms e x h i b i t t y pe c h a r a c t e ri s t i c s wi th the e x c e p t i o n o f the c arbo n p r e p ared wh e n S i R=0：1 i n d i c a t i n g tha t the S S TCM c arbo n s ar
49、e t y p i c al me s o po rou s mate r i als Hy s-t e r e s i s i s c l e arl y v i s i b l e in the reg im e o fme s o po re fil l i n g an d s h o ws Hl c h a r a c teris ti c s whic h c an be a t t r i b u t ed t o 维普资讯 http:/ 塑 i!e W r lK ln s p r e p a r e d b y a s im u lt a n e o t s v n th e
50、tic te m p la re c m n iz a ti。1 3 c y l i n d r i c a l p o r e s As i s s h o wn i n F i g1 a n d Ta b l e l，wi t h t he i n c r e a s i n g o f the t r e a t i n g t i me o f p r e c u r s o r s o l s o f s i l i c a t e m p l a t e，th e S B E T i n c r e a s e s s h a r p l y and th e h y s t e