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¦Ä«½»ÛÉÂ¢Äæèã°éBFig. 1(Color online) The main constructional elements of the sin­gle cell of PEMFC.

72  úËõ March 2013 Vol.26 No.2
(C) 2013 The Japanese Society for Synchrotron Radiation Researchðà ¡ ÅÌªq`R¿drÉ¨¯édÉÚÌàÉ¨¯éàG}ÌªzÉ»wóÔÌÏ@ãLÌ½®ª¦·æ¤ÉêÊÉ½êÆµÄC½K

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dÉG}FAm[h½âJ\[h½ÉKvÈG}BÂÜè PEMFC Ì­dÁ«ÉÍC½KXâ¶¬ÈÇ{eÅÍAm[hG}ÆµÄ Pd/C ðgpµCJ\[hÌ¨¿gUCvg`±x¨æÑdq`±x¾¯ÅÈ­G}ÆµÄ Pt/C â Pt3Co/C ðgpµÄ¢éBAµCJ

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é½ßÉR¿drì®ðºÉ¨¢ÄàªèªÂ\ÅLµÄ¢éBXAFS @É}ÅéÚµC2006NÉPZðp¢ÄJ\[hGd¬§xFR¿dr­dÉæèo·d¬ðdÉô½ÊéàSYfiPt/CjÌ in­situ XAFS ªèðsÏÅKi»µ½lB×Ìå«³ð\·PÊÆµÄµÁ¢CóÁd³ðÏ»³¹½ÛÌ Pt/C G}Ì Pt im±Ä¢éBqÌ\¢Ï»ð¾ç©ÉµÄ¢é7)B±ÌÊ©çúËõðpµ½ XAFS @ÍCPZàÌ Pt nG}ÌÇzÊ\¢â_»ÈÇð in­situ Åªè·éªÂ\Åé½ßC­dÉ¨¯é Pt nG}ÌóÔðð·é½ßÌ
ñíÉ­ÍÈªèè@Ì 1 ÂÅéð¦µ½B»ÝCä X Í in­situ XAFS @ ð X É PEMFC É K p ³ ¹ C

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m[hßd³æèàå«¢9)BÜ½CJ\[hd³ÍC×ª³¢êÅÍ1.0 V tßÆ­C×ð^¦½êÉ
ÍC0.6 V öxÉÜÅºªéB±ÌJ\[hd³Ìã¸Æ
º~ÌJèÔµÉæèG}±qÌnðCÃWCSÌ©çÌEÈÇªN±èCdr«\ªáºµÄ¢­B±Ì½ß½
ßd³Ìáº¨æÑG}ò»Ì}§ÌÏ_©çCJ\[hG}½¨æÑG}ò»@\Ìð¾ª]ÜêÄ¢éBä
XÍC100 ms ÌA±Ôªð XAFS ªèªÂ\ÅéSPring­8 BL40XU ðpµCPZÉ¨¯éJ\[hG}±qÌÇ\¢Ï»ðÏ@·é±ÆÅCJ\[hÉÅÌG}½¨æÑò»@\Ìð¾ÉqªéÆl¦À{µ½BªèÎÛÆµÄsÌÌ Pt/C G}Æ Pt3Co/C G}ðÌpµCin­situ Ôªð XAFS ªèÉæè¾½Ê©çC
G}±qÌ©|¯¬xèð©ÏàéðÚIÆµ½BÜ
½Cin­situ ªèÌ PEMFC Ìì®ðÍCdÉG}ª
L·é_»Ò³\ð]¿·é×ÉJ\[hÉfð¬Ê³¹CÒ³óÔÆ_»óÔÉÎ·é0.4 V Æ1.0 V Ìd³XebvðÌpµ½BÜ½CXebvÍCd¬ª®SÉ¿­90 s Æµ½BÀÛÌ PEMFC ÆÍÙÈèJ\[hÉfð¬Ê³¹½RÆµÄCdÉG}©gÌÀè«ð]¿·é×É­§IÉ_»Ò³ðs¢C»Ì_»Ò³¬x©çdÉG}ÌÀè«ð©Ïàéðæ¸Dæ³¹½×
é B ê Ê I È Pt / C G } i TEC10E50E, TKK Co.

ÅLtd.jC¾¯ÅÈ­ Pt3Co/C G}iTEC36E52E, TKK Co.
Ltd.jàp¢½ÌÍCCo ÌYÁÉæè Pt ±qÌÏv«ªüã·éªmçêÄ¢é©çÅé10)BÜ½CPt3Co/C

G } Ì Pt3Co ± q Ì \ ¢ ð Í É Ö · é ñ  ª ½ è11) CG}Ìf«ªùmÅµ½RÌ 1 ÂÅéàärG}ÆµÄÌpéB

In­situ Ôªð XAFS ªèÉÍCPZÌSªÉ
X üª§ß·éæ¤ÉGhv[g¨æÑWdÌÉð¯CZp[^ð X üª§ßÂ\Èú³ÆÈéÜÅí Á ½ P Z  ð g p µ ½ B Ü ½ C in­situ  Ô ª ð ª èÍC¬HÌ channel ÌªÉÄsÁ½Bæ 2 à®íÅéCo ÌÏ»à§ß@ÉÄÏ@ðs¤½ßCJ\[hG}Ê
ÍCÊíæèà½¢ 6 mg cm|2 Ì MEA ðgpµ½BÊíæèñíÉ½¢G}SÊÅé½ßCÏ@³êédÉG}Ì½ÉÍC¨¿gUÆdqgUÉÖ·éïR¬ªª

Fig. 2 (Color online) In situ Pt­LIII edge XAFS spectra at 0.4 and
1.0 V for the Pt/C and Pt3Co/C MEAs (60 s~3 scan). (A)Pt LIII­edge XANES spectra: blue dashed line, Pt/C at 0.4
V; red dashed line, Pt/C at 1.0 V; blue solid line, Pt3Co/C at
0.4 V; and red solid line, Pt3Co/C at 1.0 V. (B) their Fouriertransforms (Pt/C: k30_140 nm|1, Pt3Co/C: k30_130nm|1): solid line, experimental data; and dashed line, tted
data. (a) Pt/C at 0.4 V, (b) Pt/C at 1.0 V, (c) Pt3Co/C at
0.4 V, and (d) Pt3Co/C at 1.0 V.

ÜÜêéBµ©µÈªçCî{IÉG}±qãÅN±éG
}½©ÌªÏ»¹¸ÉC¨¿gUïRâdqgUïRÈ
ÇÉæèCÉâ©É\¢Ï»ªÏ@³êéÆ\zÅ«éBV ÅÍÒ³µÄ¨èC1.0 V ÅÍ_»µÄ¢éª¦´³»ÌÊÆµÄC\¢ªÏJ·éßöð»ÊµÕ­Èé

ê½BÁ¦Ä0.4 V¨1.0 V ÅÍ Pt_Pt ÌJôÆ¯ðl¶·éÆCÊíÌ 6 {ÈãÆÈéSÊÌG}w

É Pt_O ª`¬µC1.0 V¨0.4 V ÅÍ Pt_O ÌJðp¢½ªèªC»óÅÍ_ÉqªéÆ»fµ½BôÆ¯É Pt_Pt ÌÄ`¬ªsíêÄ¢éð EX­

î{IÈ\¢îñð¾é×É SPring­8 BL01B1 ÉÄ Pt

AFS ðÍ©ç©oµ½iFig. 2jB±Ìd³XebvÌ/C G}¨æÑ Pt3Co/C G}Ìd³XebvÉÎ·é\¢

Co ÉÖ·é\¢Ï»ðÏ@·é×ÉCCo K [üÓÅÌÏ»ÉÂ¢Ä²¸µ½B0.4 V¨1.0 V¨0.4 V Ìd³Xe

in­situ XAFS ª è à ¹ ¹ Ä s Á ½ i Fig. 3 jB Co K [bvðs¢ÈªçCPt LIII [üÓÌGlM[ÉÄ in­

XANES XyNg©ç Co ´qÍCCo0 æèà_»ªsitu XAFS ªèðs¤Æ Pt ±q¨æÑ Pt3Co ±qÍC0.4

­ CoO æèà_»ªá¢ªÇÝæêéBÜ½CPt

74  úËõ March 2013 Vol.26 No.2

ðà ¡ ÅÌªq`R¿drÉ¨¯édÉÚÌàÉ¨¯éàG}ÌªzÉ»wóÔÌÏ@Êð`¢ÄÁµÄ¢éBÏ»Êª­È¢ª Pt_O zÊà¯lÌXüð¦µÄ¢éBÜ½CPt_Pt zÊÍCÏ»ÊªÍ©Åéªd×ÊÌÁÉº¢¸­·éXüÉéBÎµÄCPt_Co ÌzÊÍCwÇÏ»¹¸ÉêèÁ½BÉd³ð1.0 V ©ç0.4 V ÉÏ»³¹éÆCÅO zÊÍC¸­µC
d×CzCgC³¨æÑ Pt_
Pt_Pt zÊªÁµ½Bî{IÉÍ0.4 V¨1.0 V¨0.4 V
Ìd³XebvÅÍCÂtIÉ_»Ò³½ªN±ÁÄ¢éÆl¦çêéBFig. 4 É¦·eÈüð exponential ÈüÉÄtbeBOðs¢\¢IÏ»ÉÖ·é©|¯ãÌ¬xèð©ÏàéÆC_EXebvi1.0 V¨0.4 Vj
ÌûªC¬xèªå«¢ð©oµ½B³çÉC±êçÌlÍCPt_Pt Ìð£/`¬¨æÑ Pt_O Ì`¬/ð£ÌSÄÌßöÉ¨¢Ä Pt/C G}æèà¬¢iFig. 5j
BÂÜèCPt3Co/C G}ÍCPt/C G}æèà_»Ò³ÉÎ·é½«ª¬¢ðÓ¡µÄ¢éB¾¢·¦éÆC­dÉG}ò»ÌvöÆÈè¤é_»¨wªG}±q\ÊÉ`¬³êÄà Pt3Co/C G}ÅÍdrd³ÌáºÆÆàÉÒ³³êÕ¢BÎµÄ Pt/C G}ÅÍC\Ê_»¨wªd³áºÉ¨¢ÄàÒ³³ê¸sÂtÈ_»¨wð`¬·éÂ\«ª¢12) B±Ì\Ê_»wðÒ³·é½¬xÌá¢ªCPt3Co/C G}Æ Pt/C G}ÌG}Ïv«Ì
Fig. 3(Color online) In situ Co K­edge XAFS at 0.4 and 1.0 V for
the Pt3Co/C catalyst (60 s~4 scan). (A) Co K­edge
XANES spectra: black solid line, Co foil; black dashed line,
CoO; blue solid line, Pt3Co/C at 0.4 V; and red dashed line,
Pt3Co/C at 1.0 V. (B) their Fourier transforms at k30_
120 nm|1: solid line, experimental data; dashed line, tted
data; (a) Pt3Co/C at 0.4 V and (b) Pt3Co/C at 1.0 V.

á ¢ Æ µÄ \ êÄ ¢ é Æl ¦ ç êé B In­situ Ô ª ð
XAFS @ðp¢Ä Pt3Co/C G}Æ Pt/C G}Ì{¿IÈ
_»Ò³\ð]¿µ½B¾çê½Ê©çCPt3Co/C G}Æ Pt/C G}ÌÏv«ªÙÈévöÌ 1 Âð¾ç©Éµ½BOqÌÆ¨èiæ 2 ðQÆjC½­Ì\¬Þ©ç¬è§ÁÄ¢é PEFMC ÅÍCPZàÅÌ½KXâ

LIII [ÆÍÙÈèCd³ðÏ»³¹Äà XANES XyNg¶¬

ÉÏ»ªÏ@³êÈ©Á½BEXAFS ðÍ©çàCPt_KXâ¶¬

ð¼ÚÏ@·é±Æªïµ¢Bµ©µÈªçC½
Ì®ªdr«\Ée¿ðyÚ·½ßC­dCo ¨æÑ Co_Co ªCd³Ï»ÉË¶µÈ¢±ÆÉ¨¢ÄZàÅ¶¶Ä¢é¨¿gU®ÉÎ·élª¦³ê½BùÉ Pt3Co/C G}Ì Pt3Co ±qÍC±q\XÈÂ»ZpÌJ­ªiñÅ¢é3_5)BïÌIÈÏ@èÊÉ Pt b`wðL·é Pt3Co àRA/Pt VF\¢@ÆµÄC­dÉ¨¯éPZàÌ_fª³ªzÍCé  ª ñ  ³ê Ä ¨ è11) C À Û É in­situ ª èã Ì_f´«Ffð¬HÉ«t¯éÉæèÏ@µC¶¬Å

Pt3Co/C G}Ì STEM_EDS ªèðs¤Æ Pt3Co ±qªÌ®Í X­ray computed tomography @ÉæèÏ@³Pt b`È\ÊwðLµÄ¢éàmF³ê½Bµ½ªêÄ¢éª½¢B»ÌÊÆµÄC×óÔÅÍCK

ÁÄCãLÌÊÍCPt3Co/C G}ªCPt3Co àRA/X¬üûtßÌ_fª³Éä×roûtßÌ_fª³ªá

Pt VF\¢ðLµÄ¢é±ÆÉNö·éÆ_t¯½B¢ªÏ@³êÄ¨èCÜ½Crib ªÉÄ¶¬µ½

Pt3Co ±qÅÍ Pt VFwÌÅ\ÊÉÄ_»Ò³½
ª¶¶Ä¢éÆ\z³êé½ßCPt LIII [ÌGlM[

channel ÇÊÉ«oµCæèå«ÈªHð`¬·éà

Ï@³êÄ¢éB±êçÌû@Éæè­dÉ¨¯éZÉ i è C in­situ  Ô ª ð XAFS ª è ð s Á ½ B Ü ½ C

àÅÌ¨¿gU®ª¾ç©É³êÄ«Ä¢éªC¢¾

XAFS ªèÔðd³XebvO10 s ©Âd³Xebv

ÉdÉG}ÉÖ·é¼ÚIÈóÔîñðÜñÅ¢È¢B»

ã50 s Ìv60 s ÆµCÔªð\ð100 ms àµ­Í500±ÅC­dÉ¨¯é Pt/C G}Ì Pt ±qÌ_»óÔªms ÆµÄ in­situ Ôªð XAFS ªèðÀ{µ½BIn­situzðÂ»·éðÚIÆµCSPring­8 BL39XU ÉÄ} Ô ª ð XAFS ª è É æ è ¾ ç ê ½  Ê ð Fig. 4 É ¦CNr[ð¸³¹éÅ¾½}bsO}Ìæð·Bd³ð0.4 V ©ç1.0 V ÉÏ»³¹éÆCzCgÍðsÁ½BC³ÍCd×Ï»Æ¯lÉÔÉÎµÄwÖIÈ

KX¬HoüèûtßÉ X üª§ß·éæ¤ÉGhúËõ March 2013 Vol.26 No.2  75

Fig. 4

Time proles of (1) electric charge and Pt valence on an equivalent scale, (2) CNs of Pt_Pt and Pt_
Co bonds and(3) CN of Pt_O bonds for the voltage­cycling processes on Pt3Co/C. (A) 0.4 V¨1.0 V and (B) 1.0 V¨0.4 V. k
30_130 nm|1; R0.10_0.31 nm. ~: electrical charge in the cell, ¢: Pt valence, å: Pt_Pt, {: Pt_
Co, and ä:
Pt_O. Dashed lines in (A1) and (B1) correspond to be the valence state of Pt foil. The intervals on the right andleft axes in (1) were scaled to be identical (in coulombs).

Fig. 5(Color online) Proposed structural kinetics of the surface events on the Pt/C and Pt3Co/C cathode catalysts forthe voltage cycling processes at 353 K. Each voltage­cycling process can be regarded to be reversible.

76  úËõ March 2013 Vol.26 No.2

ðà ¡ ÅÌªq`R¿drÉ¨¯édÉÚÌàÉ¨¯éàG}ÌªzÉ»wóÔÌÏ@Fig. 6(Color online) SEM images of membrane electrode assem­bly (a) and the morphology of catalyst layer (b). TEM im­age of electrocatalyst (c).

Fig. 7(Color online) I­V curve under various oxygen partial­pres­sure conditions. Circle (red): 5÷O2{95÷N2, Square(blue): 20÷O2{80÷N2.

¯CZp[^ð X üªÔÍCs[NgbvÆzû[OÌ­xÌ·ªlðzû_§ßÂ\Èú³ÆÈéÜÅíÁ½óÔªðpPZðgpÆzû[OÌ­xÌ·ªlÅÁ½liiII_I)/(III_Ijjv[g¨æÑWdÌÉðµ½BZp[^ÌKX¬HÆµÄCª 1 mmC[³ªÆµ½BÈÕIÈû@ÉÄ Pt/C G}ÌªzÆ_»óÔð

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dóµðl¶µCI zû[Oi11.527 keVjCII s[Ngª¬³¢¨æÑ Pt/C G}ª_ÉÏw³êG}wbvi11.570 keVj¨æÑ III zû_i11.600 keVjÌ

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éÆl¦çêéBÜ½C±ÌúËõ March 2013 Vol.26 No.2  77

Fig. 8

(Color online) Mapping images at before edge (11.527 keV), edge jump (mt at 11.600 keV|mt at 11.527 keV)and white line height [(mt at 11.570 keV|mt at 11.527 keV)/(mt at 11.600 keV|mt at 11.527 keV)] under N2 ow
conditions.

Fig. 9(Color online) Mapping images of white line height [(mt at 11.570 keV|mt at 11.527 keV)/(mt at 11.600 keV|
mt at 11.527 keV)] at near inlet and outlet under various load and oxygen partial­pressure conditions.

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78  úËõ March 2013 Vol.26 No.2

ðà ¡ ÅÌªq`R¿drÉ¨¯édÉÚÌàÉ¨¯éàG}ÌªzÉ»wóÔÌÏ@³ÈÇíXÌððÏ¦ÄXÈé¢ªKvÅ

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Fig. 10 (Color online) XCL­XAFS setup at BL47XU of SPring­8.

Fig. 11(Color online) Position of Pt catalyst in catalyst layer, cross­sectional SEM image and series of depth­resolved
XANES spectra. (A1) three­dimensional image of fresh MEA, (A2) cross­sectional SEM image of fresh MEA,
(A3) depth­resolved XANES spectra of fresh MEA, (B1) three­dimensional image of degraded MEA, (B2)cross­sectional SEM image of degraded MEA, (A3) depth­resolved XANES spectra of degraded MEA.

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80  úËõ March 2013 Vol.26 No.2

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depth Z of 113.2 mm for the catalyst layers in (A) fresh and(B) degraded MEA. Vertical axis (intensity) was normal­
ized by Pt LIII edge jump. Cross­sectional images represent
Pt quantity observed by XCL. (a1), (a2), (b1), and (b2)(DX27.6 mm and DY32.4 mm) in the cross­sectional
images represent measured areas of the corresponding
XCL­XANES spectra. (c) XANES spectrum of Pt foil.

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82  úËõ March 2013 Vol.26 No.2

BüÃØ©RÈw¤@\ ªqÈw¤ ¨¿ªqÈw¤Ìæ y³ö¤åw@åw¨Èw¤È\¢ªqÈwêU y³öE­mail: mtadaims.ac.jpêåF¨»wC³@»w
mªðn
2004Nåwåw@wn¤È»wêUmÛöÞC¯N 9 æè¯èC¯³Cy³öðoÄC2008N10æè»EBðà ¡ ÅÌªq`R¿drÉ¨¯édÉÚÌàÉ¨¯éàG}ÌªzÉ»wóÔÌÏ@Investigation of the chemical state and thesituation of platinum based electrocatalyst
in polymer electrolyte membrane fuel cells
Takahiro SAIDA

Institute for Molecular Science,
38 Nishigo­naka, Myodaiji, Okazaki, Aichi 444­8585, Japan

Mizuki TADA

Institute for Molecular Science,
38 Nishigo­naka, Myodaiji, Okazaki, Aichi 444­8585, Japan

Abstract

The information obtained from time­resolved and space­resolved XAFS methods were reviewed
using these experimental results in order to understand the chemical state and the situation ofelectrocatalyst under the fuel­cell operation conditions. In case of in­situ time­resolved XAFS
method, the redox ability of surface oxide layer on Pt/C and Pt3Co/C was estimated. As results,
one of the reasons that Pt3Co/C has higher durability than Pt/C was suggested. The spatial distri­bution of Pt/C in the fuel cell under the operation conditions was depicted by in­situ space­resolved XAFS method. The oxidation state of catalyst particles depended on position of gas owchannel, and it diered between channel and rib. Three­dimensional space­resolved XAFS method
revealed three­dimensional image of catalyst layer in membrane electrode assembly. These in­situ
XAFS methods help to clearly understand the black­box which is the chemical state and/or thesituation of electrocatalyst under the operation condition of fuel cell.

úËõ March 2013 Vol.26 No.2  83