ð à`ECIñdrdÉ½_Ci~NXÌóÔªzðÍ
ºRüT

såwY¯wAg{ §611_0011 s{F¡sÜ¯

kckksåwY¯wAg{ §611_0011 s{F¡sÜ¯csåwY¯wAg{ §611_0011 s{F¡sÜ¯v |»ÝgíêÄ¢é`ECIñdriLIBjÌÜdÉÍ¡GÈ 3 ³\¢ðLµÄ¨èC\Ê_WdÔÅ­¶·é[úd½isxÌÎçÂ«ÌðÆ»ÌðÁªÛèÆÈÁÄ¢éB{eÅÍC±êçÌóÔªzðIyhªÍ·×­C`10 mm I[_[Åè_Ï@ªÂ\ÈGlM[¸^¤Å_ XRD @ðJ­µ½B{@ðÀpXP[Å éú³100 mm öxÌV[gó LiNi1/3Co1/3Mn1/3O2 ÜdÉÉÎµÄKpµCfÊûüÉ­¶·é[úd½ÌÎçÂ«ððÍµ½BÜ¸C[úd½ÌÜdÉfÊÉN«é`ECIZxÌÏ»ðÀpãp¢çêéÔªð\ÅÂ»Å«é±ÆðmFµ½B»ÌãCèd¬[údÉ¨¢ÄC1C [gÜÅÍeÊ¸­ðÙÆñÇ¦³È¢ZÉKpµ½Æ±ëCæèx¢[d[gÆÈé0.5C [dÅ½úÉ½isxÉ·ª¶¶Ä¢é±Æª¦³êC»Ì·ÍdðtZxÉå«­Ë¶·é±Æªí©Á½B

à®_»¨iRog_`EÈÇjÌ³ÉÆÌÔð[1. Í¶ßÉ

údÉºÁÄ`ECIªoüèµCCIÚ®ÆdßNC±Â\ÈÐïÌ\zªdv³êCGlM[

qÚ®ªÎÉÈÁÄisµÄ¢éPÈ_»Ò³½ÅÌÀè»Cø¦»âÂ«×á¸ÖÌæègÝªÏÉIÉsíêÄ¢éB±¤µ½ÐïóµÌÈ©ÅCÆêðIÎ¸ÉGlM[ÌÛ¶ÆæèoµªÂ\ÈñdrªÚ³êÄ¢é1,2) B»ÝCL­gíêÄ¢éñdrÉ`ECIñdriLi­ion battery; LIBjªèC¬^»CyÊ»Æ¢¤ZpJ­ð«Á©¯ÆµÄC|[^uRs[^ÈÇ½­ÌgÑ^dq@íÅ@\»C«\»ªiÝCÊÆµÄ±êçÌ@íÍ­IÈyð°½3_5)BÈé LIB ÌprÆµÄÍCÔÚpÈÇªi³êÄ¨èC]Éä×ÄGlM[eÊÌå«¢drÌJ­ªißçêÄ¢éB
LIB Ìå^»ÍC½¾PÉdÊâeÏªå«­Èé¾¯ÅÍÈ­CLIB Ì\¬ÉR·é»Ûªæè°É»êÄµÜ¤Æ¢¤Ûèðø¦Ä¢éB¾¢·¦êÎC»êÍ LIB Ì[úd½ÅÍÈ­C»ÝCÀp»³êÄ¢édrª{¿IÉÁÄ¢é»ÛÅèC¡ãCÀpdrÌ

«\üãÌ½ßÉ»Ìð¾ª]ÜêéB LIB Ì\¬ÉR
·é»ÛÉÂ¢Äq×éOÉCLIB Ì[úd½Ì´ÆÀÛÌ LIB ÉgíêédÉÌ\¬}ð»ê¼ê Fig. 1
ÉÍ®IÉ¦·BFig. 1a Ìæ¤ÉCLIB Ì[úd½ÍCYfÞ¿iOt@CgÈÇjÌÉÆ`EÜLJÚ

Fig. 1(Color online) Schematic diagrams of (a) LIB and (b)cross­section of composite electrodes.

úËõ July 2015 Vol.28 No.4  161(C) 2015 The Japanese Society for Synchrotron Radiation ResearchéB±êÉÎµÄCFig. 1b Ìæ¤ÉÀpdrÅÍC`E
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materialjÍC¼a\ mm ©ç mm ÈºÌ½»²ªgíêC¨¿ÔÌdq`±ðâ·é½ßÉ±dÜÆÄÎêéJ[{÷±qð¨¿²ÆêÉ¬ºí¹ÄÜÅÅèµCWdÌicurrent collectorjÅ

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ðmÛµÄCCIÚ®ÆdqÚ®ðø¦æ­¼§³¹éððÊ½µÄ¢éBµ©µÈªçCTCYà§xàÜ¿Ü¿È±qÌ¬óÔÅéÜdÉÌO³\¢ÍsÏêÅ¡GÈ½ßC¨¿»ÉE£É}ü·é`ECIÊªÜdÉàÅóÔªzðÂæ¤ÉÈèC´IÉÍPÅéÍ¸Ì[úd½ðdràÅ¡GÉµÄ¢éB»ÌÊCdÉÉ¢½ªª¶¶â·­ÈéÆCÁÉ¢d¬§xÉ¨¢ÄÍd³âeÊÌáºCÂÜèoÍáºðµ¢ÄµÜ¤Bµ½ªÁÄCLIB Ì«\üãÉÍCÜdÉÌ¡G
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ðÛÂæ¤ÈdÉÝvªßçêéB±êÜÅÍCo±ÉîÃ­ÝvªåÅÁ½ªC³çÈé«\»ÉÍÀEªFig. 2(Color online) (a) Changes in lattice parameters of
LixNi1/3Co1/3Mn1/3O2 and (b) typical changes in theinterplanar spacing of the (113) planes.

éB»±ÅCdÉà½ÌóÔªz­¶ÌJjYð¾ç©ÉµC»Ìm©ÉîÃ¢ÄKØÉÜdÉðÝv·é±ÆªdvÆÈéB»Ì½ßÉÜ¸CäXÍ®ìºÉéB»±ÅCTvOÆoíOÉ»ê¼ê_uXé LIB àÅ­¶·é[úd½ixÌóÔªzðÂ»bgðÝuµÄCüËXbgÆóõXbgÅ`¬³ê·éªÍû@ðJ­µ½B»ÌãÅC»ÝÌ LIB ÅÅàé¤Å_¾¯ªÏ@ÍÍÆÈé¤Å_ XRD @ðÌp·êé LiNi1/3

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Co1/3Mn1/3O2 ÌÜdÉðp¢ÄZðì»µC»ÌdÉæÁÄñÜðªè·éÆCô½wIzuªÏ»·éÌÉrÁ«ÆdÉfÊàÉ­¶µ½½isxÌóÔªzðäºÁÄCÏ@ÍÍàÏíÁÄµÜ¤½ßCÏ@Êu¸xªæ­p¢çêÄ¢é³É¨¿ÌÐÆÂÅ

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162  úËõ July 2015 Vol.28 No.4

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SPring_8 Ì BL28XU ÉÝu³ê½ªèuÌCAE
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mN[^ÌpxÉæé X üÌ³Ï»ð©ÏàéÆmN[^º¬ÉÝuµ½ñ17 m ÔuÌ_uXFig. 4 Ìæ¤ÉÈèCmN[^Ìpxª6ÈºÅéÌÅC®(1jÉ]ÁÄbgiTC Xbg 2 Æ TC Xbg 3FXbgÍr[ÍC³Ï»Í50 mmÈºÅTCYæè[ªÉ¬³¢jðÊÁ½½s«Ì¢PFõ

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Fig. 3Fig. 4

Estimated changes in the exit­beam height from the compact
monochromator with a Si111 channel­cut crystal and a 3_
mm gap calculated using equation (1). The exit­beam
heights are plotted at 1 keV intervals between 38 keV and 6
keV.

(Color online) A schematic layout of the energy­scanning confocal XRD equipment on BL28XU at SPring_8.

úËõ July 2015 Vol.28 No.4  163

aª 1 m ÌñÜvðp¢ÄCüË X üÌÊuÆ­UpðX üÆoíªÎÌzuÆÈéæ¤É¤Å_ð`¬µeGlM[Åªèµ½Êð Fig. 5 É¦·B±Ì}©ç

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iLjÉàÖíÁÄ¨èC»ÌlÍ 1/sin u Éäá·éBu±ÌÙ©ÉCu ÌlÍ X üª¿ð§ß·éiü·óÔªð\GlM[¸^¤Å_ XRD @ÅÍC¤Å_Ìô½w

Ìlð¬³­·éÆCiü·ª·­ÈèCTvÌ©È

IzuªCóÔªð\ðnßÆµ½¢­Â©ÌªèðÆzûªÁ·éB»Ì½ßC¢óÔªð\ð¾æ¤Æ u§ Ú É Ö W µ Ä ¢ é B { ¤  Å Í C Fig. 6a, b Ì æ ¤ ÉÌlð¬³­·éÆ©ÈzûÉæé X ü­xÌ¸ªåV[góÌ¿ð«­ÈèCñÜÌM­xªã­ÈéÌÅCÔªð\ª½ûüÉZbgµ½½ËzuÅCüË

]µÉÈé±Æàé¢¤g[hItÌÖWÉ

éB³çÉCu ÌlðÅèµÄGlM[¸ÉæÁÄñÜ
XyNgðªè·é{@ÅÍCüË X üÌGlM[CÂÜèmN[^pxium jÆ¿ÌiqÊÔuÍC®(2)ÌÖWÅ\³êéBdhkldSi111~sin um sin uµ½ªÁÄCu Ìlðè·éÉ(2)½èCóÔªð\C©ÈzûÉæé X ü­xÌ¸CubO½ËÌðª
Ï@¿ÉÎµÄÅKÆÈéæ¤Él¶µ½BFig. 5(Color online) Intensity proles of the direct beams throughthe incident and detecting slits, which were set at a height of
30 mm. The intensity proles were measured using an ion
chamber at 1 keV intervals in the energy range between 20
keV and 38 keV.

Fig. 62.4

ñÜvt@CÌs[Nªð\u ÌlðêèÉÛ¿CGlM[¸ÉæÁÄ¾çêéñÜvt@CÌs[Nªð\iDd/djÍCªõfqÌàÂGlM[ªð\iDEjÆ X üÌ­UpiDujÉ(Color online) Sketches of cross­section of positive composite electrode with incident and diracted beams, slits,
and YAP detector and schematic view of the lozenge­shape probe gauge in the cross­section of the electrode.

164  úËõ July 2015 Vol.28 No.4

ðà ¡ `ECIñdrdÉ½_Ci~NXÌóÔªzðÍæÁÄ®(3)Ìæ¤É\³êéB| d || E |{|cot u|Du
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±±Å¾¤ªõfqÆÍC{@ÅÍmN[^Ì±ÆÅèCæÉq×½g·ªU XRD @ÅÍCá¦Î Ge ¼±ÌoíÌæ¤ÈGlM[ªð\ÌÅéoíÌ±ÆéBDE/E ÉÎ·é Si(111)`lJbgmN[^Å¾çêéPF«ÍCêÊIÉ10|4 I[_[ÈÌÅCGe ¼±Ìoíæèàñ10{Ì¢GlM[ªð\ÅéÆ¢¦éBÉCX üÌ­UpÍõ¹©çÌ­UÆSjI¼aÆXbgTCYÅ«Üéô½wIÈ
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Fig. 7a É LiNi1/3Co1/3Mn1/3O2 ÌÜdÉÌGlM[

Fig. 7(Color online) XRD data for the cell containing the
Li1Ni1/3Co1/3Mn1/3O2 electrode. (a) Energy­scanning confo­
cal XRD spectrum with the result of pattern matching and(b) angle­scanning XRD pattern.

Table 1

Dd/ds obtained by the energy­scanning XRD spectrum andthe angle­scanning XRD pattern shown in Fig. 7.

¸^¤Å_ XRD XyNgð¦·B±ÌÆ«C_u
XbgÌcTCYÍ50 mm Æµ½BÜ½CñÜ­xÍCüËõ­xC¿Éæé©ÈzûCoí´xÌGlM[Ë¶«Ì

ép[^Æ[cÎõöqÅKi

»µ½B±êð Fig. 7b É¦µ½üËõGlM[ª29keV Åpx¸ÉæÁÄªèµ½ñÜp^[Æär·Energy­scanning

Angle­scanning

Millerindices

d/Å

Dd/Å

Dd/d

d/Å

Dd/Å

Dd/d

ÚêvµÄ¢é±Æªí©éB±ÌñÜXyNg©ç¾

015

1.871

0.00680.00361.870

0.00620.0033çê½s[Nªð\iDd/djÍCñ0.0033Å

009

1.581

0.00560.00351.581

0.00740.0047107

1.573

0.00600.00381.573

0.00590.0038018

1.446

0.00430.00301.446

0.00500.0035110

1.432

0.00410.00291.432

0.00430.0030113

1.371

0.00420.00311.371

0.00420.0031éÆCTable 1 Éà¦·æ¤ÉCs[NÊuC¼lªÙèiTable1jCæÉ®(3j©çß½s[Nªð\0.0004æèàu[hÉÈÁÄ¢½B±Ì±ÆÍCªèf[^Ìs[NÍC¿Ì»«ÈÇÌîñð¨¦½ÊÅèC¤Å_

XRD XyNgªèuÍC[ªÉ¢s[Nªð\ðÁÄ¢é±Æð¦µÄ¢éÆ¢¦éBÆèí¯C107Æ
009, 108Æ110Ìæ¤ÉiqÊÔuÌ·ª¬³¢×èÁ

¾çêéTCgèL¦ÈÇÌl©çCèÊªÍàÂ\É½s[NÌª£ªÅ«Ä¢é±ÆÍCiqèÏ»©çÈéÆúÒÅ«éB

LIB Ì[úd[xðªÍ·éÆ¢¤{¤ÌAv[`ÉÆÁÄÍCñíÉdvÅ

èCTable 1 É¦µ½s[NÊuÉæÁÄiqèÍCa2.8637(5)Å, c14.238(3)Å Æßçê½B³çÉCFig. 7a ÉÍ WinPLOTR vOðp¢ÄC

3. [údßöÉ¨¯é`ECIÊÌóÔªzÏ»±±ÜÅÉq×Ä«½GlM[¸^¤Å_ XRD @p^[tBbeBOµ½ðÍÊÉÂ¢Äà¦·B±

ðp¢ÄCÜdÉàÅÌ[úd½isxÌóÔªzð±ÅÍÖXIÉSªèÍÍÉÂ¢Ä²×éÉéÁèÌGlM[ÌPFõi±±ÅÍ25 keVjðÝèµÄðÍµ½BðÍ½èCÁÉV[gódÉÌúÝifÊjûüC

ÂÜè\Ê_WdÔÌóÔÉÚµ½BÈºÈçCLIB

ÊÌ R öqÍC»ê¼ê Rp28.3÷, Rwp43.3÷, andÌ[úd½ÍC³ÉÌ¨¿»É`ECIªx 2 ((Rwp /Rexp )2 )1.32Å

oüèµCCIÚ®ÆdqÚ®ªÎÉÈÁÄis·éÌÁ½ÌÅCªèf[^ÆvZf[^Ìs[NÊuÍæ­êvµÄ¢éÆ¢¦éB{ÅC`ECIÌÉùvTChÅ

éÎÉÍCPFõÌGlM[ð¸µÄ¾½ñÜf[^ððÍicounter electrode)ÆdqÌÉùvTChÅ

éWd·éÉÍCvOÌÏXªKvÅéÌÅC¡ãC»Ì_ÉÂ¢Äà¢ðißÄ¢¯ÎC[gxgðÍÅÌÔÅCIÆdqÌÚ®ÌoXªæêÄ¢é±Æ
ªzIÈóÔÅ

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2002 N ß E å w  H w  à ® H w È ²ÆCOH©®ÔHÆ®ïÐÅ i_MIEV Ìì®p`ECIobe[ÉÖ·é¤ÉJ­É]B
2012N 4 C¯Ð©çvV^~dræ[Èwîb¤ÆiRISING vWFNgj
ÖoüB

Visualization of electrochemical reactions in oper­
ating electrode of Li­ion battery
Haruno MURAYAMA

Oce of Society_Academia Collaboration for Innovation, Kyoto University,
Gokasyo, Uji, Kyoto 611_
0011, Japan

Koji KITADAOce of Society_Academia Collaboration for Innovation, Kyoto University,
Gokasyo, Uji, Kyoto 611_
0011, Japan

Katsutoshi FUKUDA

Oce of Society_Academia Collaboration for Innovation, Kyoto University,
Gokasyo, Uji, Kyoto 611_
0011, Japan

Abstract

Spatial variations of Li­ion concentration in cross section of composite electrodes in Li­ion batte­ries (LIBs) owing to their complex structures were investigated under operation condition. To
visualize spatially­inharmonious electrochemical reactions occurring in the sheet­like composite
electrodes with a thickness of 100 mm, we developed spatial and time­resolved spectroscopic X_
ray diraction (XRD) analysis that uses continuous irradiation with monochromatic X_rays using
a confocal setup as a direct observation technique. Their position sensitivity, spatial­resolution,and prole resolution were carefully evaluated from a pre­measurement using references andmodel electrode. Then, this method was applied to operand analyses for the practical LIB cells
composed of LiNi1/3Co1/3Mn1/3O2 known as one of the most common active materials for the posi­tive electrode of LIBs. The spatial variations of Li­ions in the cross section of composite electrodes
were successfully determined with a depth resolution of 30 mm during cell operation. On the basisof the results from the newly developed analysis, we discussed eect of the electrolyte concen­
tration (LiPF6) on Li­ion transportation from the counter electrode side to the current collector side
during the operation.

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