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NHIN Rfl THS GIOI

SV DUNG ONG NANO CACBON BIEN TINH TRONG PIN DSC

Pin DSC siir dung chat mau nhay quang la the hg pin mat trdi m6\ thu hut s^ quan tam cua nhieu nha khoa hoc. Tuy nhien, cdng suS't thap va chi phf san xuat cao la nhffng rao cSn \&n Ai co thg' difa pin DSC ifng dgng vao thiTc tg'cupc sa'ng. ViTa qua, cac nha khoa hpc thuoc Dai hoc Bach khoa Nanyang, Singapore da tim ra mot phircfng phap mdi, bie'n tmh cac o'ng nano cacbon (CNT) nhim thay the'cho oxide din dign trong sud't phA trgn dg'thuy tinh din cua pin DSC, giup ha gia thanh sdn xua't.

Khai quatve pin quang dien Trong rat nhieu van de ma nhan loai dang phai doi mat, dd trO nang iLfdng va phan bo nang lUOng la nhiJng van de quan trpng nhat. Khi nguon nhien lieu hoa thach dan can kiet, ngu'di ta bupc phai chuyen hudng sang cac nguon nang lUdng thay the khac nha nang lUdng hat nhan, nang iL/dng gio, nang iUdng thuy trieu, nang ladng mat trdi...

Trong dd, nang lUdng mat trdi la nguon nang li/dng cd ban nhat, phong phu va dac biet la sach, khong gay 6 nhi§m moi trudng. Vi the rat nhieu nghien cCfu da dUdc trien khai tCf the ky XIX cho den nay nh5m cd the khai thac nang iLfdng mat trdi mpt each hieu qua va tien ldi.

Nam 1839, nha vat ly ngLTdi Phap A E Becquerel da kham pha ra hi§u ifng quang dien, cho phep chuyen hda mot phan nang iLTOng mat trdi thanh dien nang. Ke tCf do, cac the he pin quang dien (con goi la pin mat trdi) lan lupt dUdc che tao va thCf nghiem trong sudt khoSng thdi gian dai. Cho den nam 1991, hai nha khoa hoc Gratzel va O'Regan da Idn dau tien che tao thanh cong pin mat trdi tam chat mau nhay quang (pin DSC), mot the he pin mat trdi mdi hCfa hen

ti'nh u'ng dung cao va chi phi canh tranh vdi pin mat trdi dL/a tren chat ban din silic. Day dUdc xem la mot phat minh dot pha ve cong nghe nang Iddng cua the gidi 6 thdi diem bay gid, dem tai cho GS Gratzel giai thLfdng cong nghe thien men ky nam 2010 [1].

Cau tao cua pin DSC bao gom cac thanh phan sau (hinh 1): (1) dien cue anode la mang nano oxide TiO^ dddc thieu ket va gan tren mpt de thuy tinh dkn (dUdc t?o thanh tCf thuy tinh co phu mgt Idp mong cac oxide dan trong suot - TCO); mang anode oxide 110^ nay dUdc h§'p phu ddn ldp chat mau nhay quang (dye); (2) dien cdc cathode (dien cue doi) la ldp Pt di/dc phu tren mpt de TCO khac; (3) giOa hai dien ciic la dung dich dien ly chiJa cap oxi hda/khii IgVI- [1]. Nhu vay khi dLfdc chieu xa, cac phan ttf thud'c nhudm 6 trang thai cd ban (ki hieu

Hinh 1 • ciu tqio va cd che host ddng cua pin DSC

S) se hS^p thu photon va chuyen len trang thai kich thich (S*). S* 6 trang thai kich thich cd miJc nang lupng cao se tiem dien ti!f vao vung din (CB) cua TiO/(1). Didn ti!f khi do se di chuyen sang mang xdp TiCj, den de thCiy tinh din TCO roi ch§y ra mach ngoai de tai ve dien cdc ddi cathode. 6 dd dien tD se ket hdp vdi lg- tao I (2). T dddc hoan nguyen trd lai I3 nhd kb^ dang oxi hda cua chat mau nhgy quang S*

(3). CiJf thd cac qua trinh se dUdc lap lai nhu mdt vdng tudn hoan va tgo ra dong dien.

S + anh s a n g ^ S ' + ^ T p 2 (1)

l3. + 2 e ^ 3 l - (2) 31- + 2S* -> I3. + 28 (3) Chinh nhd cau tao ddn gian va nhij'ng tinh chat dac biet tren, pin DSC ngay lap tufc da thu hut si^

chu y rat Idn cua cpng dong khoa hpc. Nhieu nghien cufu ke thCfa da lien tuc dUdc thi/c hien nhim nang cao hieu suat pin, hg gia thanh sSn xuat, cung nhU cai thien cac tinh chat truyen dan cija pin. Trong d6, ck\ thien de thuy tinh din cua pin DSC la mpt trong nhOfng hUdng nghien ciJu khk thi va thu hut.

Cai thien jteuiiiy linh din De thCiy tinh dan v6n dddc ciu tao bdi mpt tam thuy tinh cd b l mSt

Tap chf KHOAHOC ,..

CdNGNCHEVlETNiSf ^o i s nam 2013

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NHIN RR TH€ GI61

dL/dc phCi mdt Idp mdng oxide din dien trong sudt (TCO). De dap Ung nhu cau sCl dung cho DSC, TCO phk\ thda man cac yeu cau sau:

CO dd trong sudt cao de anh sang truyan qua, cd dien trd thap de dan dien tdt. Mpt trong nhOng TCO dap Ung tdt c^c ydu cau tren la thiec oxide pha tap indium hoac thiec oxide pha tap fluor. Tuy nhien, cac vat lidu nay van cdn nhieu han che [2, 3], trong do gia thanh cao la mdt trong nhQng han che noi bat.

Gan day, sU thanh cong trong dieu che cac Idp mang mdng din dien va trong suo't dua tren nen t^ng cac dng nano cacbon (CNT) va graphene da md ra mdt kha nang nghien cUu mdi, thay the cac vat lidu TCO truyen thdng [4, 5]. So vdi thiec oxide pha tap fluor, sCf dung vat lidu dua tren CNT cho phep giam dang ke chi phi san xuat nhd vao ngudn cung cap cacbon phong phu va khk nang s§n xuat tU dung djch [6]. Bdn canh do, CNT cd dp bdn hda hpc cao, co dp cdng cd hpc Idn [7]. Chung cdn gan nhU trong sudt trong vung can hdng ngoai, tinh chat ma cac TCO truyen thdng khdng cd [3]. Nhflng yeu td nay khien cho CNT va grapheme trd thanh mdt trong nhUng flng vign tiem nang flng dung trong pin DSC.

Tuy nhien, cho den hien tai, viec sijf dyng CNT de lam dien eflc anod trong pin DSC gan nhU la khdng thi do khk nang xuc tac cho cac ph^n Lfng oxi hda khfl cfla CNT.

Chung cho phep cac electron thu thap dupc d anode tai ket hdp vdi IJ' tgi be mSt tiep xuc giufa anode va dung dich dien ly bang phan flng (4):

I3- + 2e- ^ 31- (4)

de che tao anode. De giai quyet van de nay, nhdm nghien cflu cija giao sfl H.V. Demir va cac cdng sfl tgi Vien Ky thuat Dien va Dien tfl, Dai hpc Bach khoa Nanyang, Singapore da de nghi mdt phUdng phap ddn gian, sfl dung CNT lam anode vdi be mat dfldc bien tinh bdi mdt Idp oxide mong, nhSm lam giam qua trinh taj ket hdp dien tfl vdi lg' trong khi vln bao toan dfldc nhflng tinh chat dien va quang cua CNT. Mac du phfldng phap nay cd the giai quye't dfldc van de, nhUng viec tim kie'm dUdc mot oxide ly tfldng de bien tinh lai khdng ddn gian. Chang hgn, mang mdng ZnO tong hdp bang phUdng phap sol - gel da dfldc chflng minh ed do trong sudt rat cao, chuyen dieh dien tfl td't trong mdi trUdng hiJu cd cua pin mat trdi [9] nhung ZnO Igi khong phu hdp vdi Idp hdn hdp anatase chfla acid trong pin DSC va dung djch pham nhudm. Tfldng tiJ, mdt Idp TiOg day dgc dieu che bdi phUdng phap phun nhiet phan cd kh^ nang chdng chiu acid nhflng Igi cd ibi oxi hda CNT 6 nhiet dd cao trong qua trinh ke't tinh mang [10].

Gan day, nhdm nghien cflu cua giao sfl H.V. Demir [11] da thflc hien bien tinh be mat cua mang mong CNT tren dien ciJc anode theo mpt phuong phap mdi: tong hdp Idp phim CNT vdi titan sub- oxide (TiO^) dUdc phu len d nhiet dp thap (150°C) bang qua trinh sol - gel. PhUdng phap nay da dem Igi nhiJng ket qua kha quan, cho phep giam gia thanh va nang cao hieu nang cfla pin DSC mdt each rd rang.

Che tao pin DSC vol dien cue phii CNT vd Tip,

hdp Idp mang mong CNT gan tren de thuy tinh bang phUdng phap sol- gel. Mdt dung djch huyen phu CNT 2 mg/ml dUdc khuay tron vdi dung djch nfldc chfla chat hoat ddng be mat sodium dodecylbenzene sulfonate vdi nong dp 0,5%, sau do hdn hdp dUdc danh sdng sieu am d 120 W nhim thu dfldc mdt hdn hdp dong nhat [12]. Toan bd hdn hdp nay dUdc cho vao sung phun va dfldc phun phfl deu len be mat kinh thuy tinh vdn se dfldc sfl dung lam de thuy tinh din trong pin DSC.

Tam thuy tinh sau dd dUde nhung ngap trong nudc trong sud't 24 gid de logi bo hoan toan chat hoat ddng be mat va cudi cung dflpc lam khd tfl nhien d khong khi. Hinh 2 the hien be mat cua de thuy tinh din sau khi da phu CNT, cho thay cac CNT vdl be day khoiing 20-25

Do dd, CNT ch? mdi dfldc sfl Qua trinh che tgo pin DSC cua dgng lam dien eflc cathode de thay nhdm nghien cflu de'n tfl Dai hpc thd Pt dit tidn [8], gin nhu khdng cd Bach khoa Nanyang trli qua ba giai mdt logi pin DSC nao sfl dung CNT dogn chinh. Dau tien, nhdm tong

Hinh 2 hinh inh ldnh hien vi diSn lO cua bS mSt de thOy tinh din sau *c/i/ phu Idp CNT

nm dUdc phu tren be mat mdt each ddng nhat vdi dp phu cao, rat thich hdp de sfl dung trong pin DSC

Giai dogn thfl hai la tdng hop Idp sub-oxide TiO^ phu len be mat cua CNT. Dung dich titanium (IV) isopropoxide dfldc trdn lan Ifldt vdi 5 ml 2-methoxyethanol va 0,5 ml ethanoiamine trong mdt binh eau 3 CO. Hdn hdp dung djch nay dfldc dun hoan luu d 80°C trong 2 gid va 120''C trong 1 gid [13] de hinh thanh ldp gel TiO,. Sau dd, Idp gel se dUde phfl quay tren de thuy tinh din d td'c dd 3.000 vdng/phut.

Be day cfla Idp phim hinh thanh

TopcH *

S6 18 nam 2013 p/^^tiZr:^- 39

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NHIN Rfl THe Gidl

dfldc dieu chlnh bdi dung djeh 2- methoxyethanol. Sau cung, toan bd de thuy tinh se dUdc nung 6 ISCC sudt 1 gid trong khdng khi de chuyen hda hoan toan gel thanh TiO,.

Dd thfly tinh dfldc phu CNT va TiO^ se dfldc si'.f dung lam didn eflc anode de ehe tao pin DSC trong giai doan cudi cung. Nhdmjighien cflu lan Ifldt phu chat ban din TiO^

Idn dien cUc anode vfla tong hop, cho TiO^ hap phu pham nhudm cis-diisothioeyanato-bis(2,20- bipyridyl-40-dicarboxylato)rutheniu m(ll) bis(tetrabutylammonium) rdi ghep vdi dien cue cathode la kim logi Pt. 6 gifla hai dien cUc nay, nhdm nghien cflu tien hanh bdm vao dung djch dien ly l^/l de tgo thanh pin DSC hoan chlnh.

Tinh chat ciia pin DSC sau khi che tao

Pin DSC vdi anode phu CNT va TiO^ sau khi dfldc che tao dUdc so sanh eac tinh chat quang dien vdi pin DSC chi sfl dung anode cd phu CNT. Cac thdng sd nhfl ddng ngan mach 1^^, the mach hd V^^, thfla so lip diy ff (fill factor) va hieu suat chuyen doi quang nang cua hai loai pin lan lUdt dUdc do trong mot he gia lap anh sang mat trdi vdi bflc xa AM1.5G (100 mW/cm^). Hinh 3 trinh bay eac ket q u i thu dfldc sau

• . . OiphOCNT

— OS phu CNT v t n o .

^

khi khao sat tinh chat quang didn cua pin.

Pin DSC vdi anode chi phiJ CNT cd cac gia trj 1^, V^^, ff va hieu suat chuyen ddi quang nang lan Ifldt la 0,281 mA/cm^ 0,057 V, 23% va gan 0%. Ket q u i nay cho thiy, pin gan nhfl khdng hogt ddng dUdi anh sang mat trdi. Ngfldc Igi, vdi pin DSC cd anode phfl CNT va TlO,, cac gia trj 1^^, V^^, ff lan Ifldt la 6,547 mA/cm^, 0,644 V, 43% va hieu suat chuyen hda quang nang dat 1,8%, chflng to viec phfl TiO^ len CNT da khac phuc hoan toan nhfldc diem cua CNT khi sfl dung trong anode cua pin DSC. Nhd phu mdt Idp TiO, ngan can Idp CNT tren de thuy tinh tie'p xuc true tiep vdi dung dich dien ly I3/I, cac electron sinh ra tfl qua trinh quang hda se dUdc truyen den CNT va khdng tham gia phan flng khfl I3-, sd IUdng electron di chuyen ra mach ngoai vi thd khdng bj suy gilm, dam bao cho pin DSC hoat ddng td't (hinh 4).

Hinh 3- gian d6 thi hiin tinh chat quang di$n cua pin DSC dUdc chS tao tii anode phu CNT vi anode phu CNT vi TiO

Hinh 4: qua trinh chuyen dien tCt td CNT den dung dich dien ly trin dien cUc anode phu CNT (a) vi si/ ngdn cin qua trinh dich chuySn dien til nay tren dien cUc anode

phO CNT vi TiO^ (b)

Nhflng ke't q u i nghien cflu cua giao su H.V. Demir va nhdm cua dng da md ra mdt tiem nang rat Idn cho viec Ung dung CNT vao pin DSC, giai quye't hoan toan van de xuc tac cua CNT ddi vdi cac phin flng 0x1 hda khfl trong hd dung djch dien ly cfla pin. Cac CNT khdng ch?

cd gia thanh thap hdn TCO truydn thdng ma eon cd nhflng tinh chat flu vidt hdn. Chinh vi vay, trong

tUdng lai, nhdm con hfldng den viec thay thd c l dien eflc cathode Pt bang dien eflc co phu CNT [14].

Neu thanh cdng, day se la mdt dot pha rat ldn trong cdng ddng khoa hpc noi chung va nhflng ngudi lam nghien cflu ve pin ndi rieng, khi ma gia thanh san xuat pin DSC chfla bao gid la thap •

LTK (tdng hdp)

Tai lieu tham khao

[ I ] K E J a s i m , Dye sensitized solar cells - working pnnciples, challenges and opportunities, www.intechopen.com/boQks/

solar-cells-dye-sensitized-devices (2013).

[2] S.R Forrest, Nature 428, 911 (2004).

[3] L. H u , D.S. Hecht and G. Gruner, A p p l . Phys. Lett. 94, 081103 (2009).

[4] Z W u , Z. C h e n , X. Du. J.M. Logan, J. Sippel, M. Nikolou, K. Kamaras, J.R.

Reynolds, D B Tanner, A.F. Hebard and A.G. Rinzler, Science 3 0 5 , 1 2 7 3 (2004)

[5] X Ll, Y Z h u , W. C a i , M Borysiak, B.

Han, D C h e n , R.D. Finer, L. Colombo and R.S. Ruoff, Nano Lett 9, 4359 (2009).

[6) B. D a n , G C. Irvin and M Pasquali, A C S Nano 3, 8 3 5 ( 2 0 0 9 ) .

[7] E. Frackowiak and F B e g u i r , Carbon 39, 937 (2001).

[8] H. Z h u , H. Z e n g , V. Subramanian, C. Masarapu, K H Hung and B. Wei, Nanotechnology 19. 465204 (2008).

[9] A K.K. Kyaw. X.W S u n , C Y . Jiang, G.Q. Lo, D.Vtf. Zhao and D.L. Kwong, Appl.

Phys. Lett. 9 3 , 221107 (2008).

[10] U. B a c h , D Lupo, P. Comte, J.E. fwloser, F. Weissortei, J. Salbeck, H.

Spreitzer and M. Gratzel, Nature 395, 583 (1998)

[ I I ] A . K . K . Kyaw, H Tantang, T. Wu, L. K e . C P e h , Z . H . Huang, X.T. Zeng, H.V.

Demir, Q. Z h a n g and X.W. S u n , Appl. Phys.

Lett. 9 9 , 021107 (2011)

[ 1 2 ] H . Z G e n g , K K Kim, K P S o , Y S Lee, Y. C h a n g and Y . H , Lee, J. A m . Chem.

Soc 1 2 9 , 7 7 5 8 ( 2 0 0 7 ) .

[13] K Lee, J Y K i m , S H. Park, S.H.

K i m , S. Cho, and A . J . Heeger, Adv. Mater 19, 2 4 4 5 ( 2 0 0 7 )

[ 1 4 ] h t t p 7 / w WW. s c i e n c e d a i l y . c o m / releases/2012/03/120314095553.htm

an TapcwKHOAHCtt „ .

*" CONGNGHE VIET NiW ® ° ' ^ "^^ ^°' ^

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