( j gh 0 /2= 'e :/2 ? ?f/2 - kaken...x^300 ºcx > d ðd ë q ñ 9 # )1 òh gj t ñä3(c) ò...

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(J - GH 0/2='E:/2??F/2& # čĠǷǺĎǺĿǸǵĸŲè ƆƑĠŊ]ŏƵDZÜıDzǼ łƆƑǂǮX^dzDZH - DzăǫĝlƉPĴƷŮlj]×ĠlƀĦNTǴK2NiF4 ê ǙËŮ]ŐǑ\HƷÄǘ¿NTĴƷǙśƛËŮ]×Ġ\ĠÇNdzăǫ ĝlŀPiLYlÀcWƶ½NTǴMg\dzs|r]µƛƥī\fUWǙśƛËŮ] ÚŀǛYǘ¿lÂĘXIiLYHĹgGY[hdz£ĕ]ǙśƛËŮlí\NTŮ ljĩƜ]ĦǝY[iƅƶlėTǴ ƆƑĠŊ]ŏƵDZƭıDzǼ In this project, we successfully synthesized transition-metal-free novel oxyhydrides that has the ordered hydride ions in the K2NiF4-type structure. The oxyhydrides exhibited the hydride ion conductivity over 150 ºC, and conductivity value increase with the introducing vacancies and interstitial hydride ions. Furthermore, the establishment of synthesis method for the controlling hydride contents and arrangement in the lattice by the cation-substitution showed a guideline for the development of new materials based on oxyhydrides. ¡¥şúǯ DZǜǯήǼ»Dz ƁĪƟLj ǠĪƟLj × ƻ ¡¥şúǯ ƆƑ¾ǚǼËø ƋƆLj]¾ƋƝƀǼŃIJËøŬœĈŎŃIJ tǼƠļòƠļŃIJor¡ī°«ă° ǶǴƆƑǟõđÀ]ƨĻ éųŧĽËeóŚŝŋ[ZdzƐ@]ŵïÝ ǮHŤÃËPidzËøÑĜlƁĪǫŚq u\ñīXIiǫŚËø~ox_] ŁĔHǰaUWDiǴŲèdz|p ŕǫ ŞeŭIJǫŞl^OcYNTƱǫżǫ~ ox]ǰĝƩ²lĦÙNTƆƑǟżHŹ ÖéXſm\ƲkjWDiHdzĂŅŽ\Ŝc gjiquþĐlǔĠPiTc\^dz ķ÷]Ʊǫżǫ]ÐŴ\ßkj[D¸JĴ ND~ox]ǟżHěƵXCiǴŸǃƧg ^dzL]ĴƷǫŚËø~ox]ûŲ\ÙK TíƈƆƑ]ƔŘǥYNWdzDZH - Dz ]orăǫŲLJ\ƄƀNTǴ )A,I12608 /21.I-96/2 /2$@I2011K2012 <D,I23655191 /2<DE"F C3 /2<DE7"F Exploration of hydride conductor /2;5 8> * EKanno RyojiF %'B4+/20! /25,I90135426

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Page 1: ( J GH 0 /2= 'E :/2 ? ?F/2 - KAKEN...X^300 ºCX > d ðD ë q ñ 9 # )1 òH gj T ñä3(c) ò ô H Uµ }\¾ NT ÓÅ ' y#5 . β ] ë q] g ±÷ lä * \ P ô ' #5 . X^ ; X ðD ë q 9 #

(�J-GH 0�/2=���'E�:/2���?��?F/2�&��

#

čĠǷǺĎǺĿǸǵĸŲè ƆƑĠŊ]ŏƵDZÜıDzǼ � łƆƑǂǮX^dz����DZH-DzăǫĝlƉPĴƷŮlj]×ĠlƀĦNTǴK2NiF4 êǙËŮ]ŐǑ�\����HƷÄǘ¿NTĴƷǙśƛËŮ]×Ġ\ĠÇNdz����ăǫĝlŀPiLYlÀcWƶ½NTǴMg\dzs|r�]µƛƥī\fUWǙśƛËŮ�]����ÚŀǛYǘ¿lÂĘXIiLYHĹgGY[hdz£ĕ]ǙśƛËŮlí\NTŮljĩƜ]ĦǝY[iƅƶlėTǴ ƆƑĠŊ]ŏƵDZƭıDzǼ � In this project, we successfully synthesized transition-metal-free novel oxyhydrides that has the ordered hydride ions in the K2NiF4-type structure. The oxyhydrides exhibited the hydride ion conductivity over 150 ºC, and conductivity value increase with the introducing vacancies and interstitial hydride ions. Furthermore, the establishment of synthesis method for the controlling hydride contents and arrangement in the lattice by the cation-substitution showed a guideline for the development of new materials based on oxyhydrides. ¡¥şúǯ � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � DZǜǯήǼ»Dz

ƁĪƟLj ǠĪƟLj ×� ƻ

¡¥şúǯ ���������� �������� ����������

ƆƑ¾ǚǼËø ƋƆLj]¾Ƌ�ƝƀǼŃIJËø�ŬœĈŎŃIJ t����ǼƠļ�òƠļŃIJ�or�¡ī°�«ă° ǶǴƆƑǟõđÀ]ƨĻ � éųŧĽËeóŚŝŋ[ZdzƐ@]ŵïÝǮHŤÃËPi�dzËøÑĜlƁĪǫŚq��u�\ñīXIiǫŚËø~�ox_]ŁĔHǰaUWDiǴŲèdz�|p� ŕǫŞeŭIJǫŞl^OcYNTƱǫ�żǫ~�ox]ǰĝƩ²lĦÙNTƆƑǟżH�Ź

ÖéXſm\ƲkjWDiHdzĂŅŽ\Ŝcgjiq��u�þĐlǔĠPiTc\^dzķ÷]Ʊǫ�żǫ]ÐŴ\ßkj[D¸JĴND~�ox]ǟżHěƵXCiǴŸǃƧg^dzL]ĴƷǫŚËø~�ox]ûŲ\ÙKTíƈƆƑ]Ɣ�ŘǥYNWdz����DZH-Dz]or�ăǫŲLJ\ƄƀNTǴ

)A,�I12608 /21.I��-96/2 /2$@I2011K2012� <D,�I23655191 /2<D�E�"F� � �����C� 3� � � � � � � � � � � � � � � � � � � � � /2<D�E7"F� Exploration of hydride conductor /2 ;5� 8>� *� � EKanno� RyojiF

%��'����B4�+��/20!� /25,�I90135426

Page 2: ( J GH 0 /2= 'E :/2 ? ?F/2 - KAKEN...X^300 ºCX > d ðD ë q ñ 9 # )1 òH gj T ñä3(c) ò ô H Uµ }\¾ NT ÓÅ ' y#5 . β ] ë q] g ±÷ lä * \ P ô ' #5 . X^ ; X ðD ë q 9 #

� ����^ 1 ²]n�r�X 1 ~ 1.2 Å ƏĐ]or�ÌēlĥVLYGgdzǰŧX]băǫHÓƩ[ǙËŮor�DZO2-DzedzǫölĥTQūǫƮYNWħiƫDƴǨ[ăǫœŐlěƵYPi����DZH+DzYřǍNWor�ăǫƐYNWǕNTůęlĥVǴMg\dzǙËǖµǫ®H-2.25 V (vs. SHE)YÍ\óIJdzŴDŽŽ\ǰq��u�þĐ]ǫŚËø~�oxlŶb½PÓƩĝlƌcWDiǴNGNdz����]or�ăǫ\ǡPiîÛ^ŗZŬJdzor�ăǫŲLJƪ°HûƾMjWD[DǴ ǷǴƆƑ]ƀŽ � łƆƑ^dz����ăǫĝlŀPiĴŮlj]żƶlƀŽYNTǴ�ùúGVn�r�]�úřĝ\�NDśƛËŮX^[JdzǙËŮ]íłŐǑ�\����lÚŀPiǙśƛËŮlŮljĩƜ]ÿLJYNTǴ ǸǴƆƑ]ĵš ����ĴƷǙśƛËŮ]×Ġ�� ŸǃƧgHLjaX\×Ġ\ĠÇNWDi ���.��êŐǑ] �'��.� lí\dz����ÚŀǛeµƛǘ¿]Ż[iĴƷǙśƛËŮ]×ĠlǀbTǴ×Ġĺ\^ǰçÆlŷDTǴ¨�\ǰç×Ġš]Áūlǐ`iǴ�=� ƂNjƎ\fiǰçƂlƁĪ×ĠXIdzČ

ç\vq�|PiLYXǰçƂlüŧ�ČçXÒh½PLYHXIiǴ�

>� ưŚç]ǰDµƛXd×ĠƘº\ĀOǏciLYHXIiǴǰçÆlŷDiLY\fUWưŚç]ǰDśƛlÑĜƘº\ǞOǏcdzǰçǰŧ�X×ĠPiLYHXIiTcdzłƆƑXƀŽYPiŮlj×Ġ\^ľǕXCiǴ�

aT?s|r�]µƛƥī\fhdz����YǙƛ]ƞĠřYµƛǘ¿lñËMRTǴMg\dz����ŔǤaT^ŌöǠ_]ǓÅ]����]ă·lǀbTǴ�����ƠļŐǑƺň�& Ƣ��ĝöƢlŷDTàĢŨúGgŌöúİeµƛǘ¿dzÖµƛ]ÏŀűlƗþËNTǴŨú^óêĭā¶Ķƽ #!5.2,��dz�ĝöĶƽ��!'5) XƲUTǴ�� ��or�ăǫű]ƿ²��\¡ţo���{�xšlŷDTǴǫö«ăĝ]ŀŬ]Ƈǁ[Zdz����]ǎűlŜciTc\ �+((�%',,2+5 šlŷDTǴ��ǹǴƆƑĠŊ����ĴƷǙśƛËŮ]×Ġ�� �'��.� ] �' l #5 XƥīNdz����]ÚŀǛ]Ż[iåũ° �'���#5��.���� �� (0 ≤ � ≤ 2)l×ĠNTƠŊdz#5 Ǜ]ðÈ\¬UWÿƍĝHijĵļDZƒǠƦ������DzGgŖĵļDZƒǠƦ��������Dz\ñËNTDZä �DzǴMg\dz

�ĝöàĢY������ƺň\fiƠļŐǑƺň]ƠŊdz����� ] �'#5�.�� �^ŐǑ�\ �.��čǬlŀNdz����H ŕµŽ\ƷÄǘ¿NWDiLYHĹgG\[UTǴ�ĵdz�' l¸W #5 XƥīNT #5��.� ��������^dzƞĠ � ≤ 1 aX^¸WǙƛXÏŀMjWDT �� ®ƥ]ƙ ���l����HÏŀNdz�ൎ\����H¾ĊNWDiLYHƇǁMjTǴ����ÚŀǛ]Ż[iƞĠ ���������� ]ÖǀIJ]ƠļŐǑlä � \ƉPǴ��

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Y�ൎ\¾ĊNT #5��.� lí\dzä \ Ɖ P Ƃ ä \ Ė U W � � � � Ŕ Ĭ Ƃ�'��α#5��α�.���α � Y � � � � Ǔ Å Ƃ�'��β#5��β�.���β �dz�'y#5����.� �β ]×Ġ\ĠÇNdz���.�� êŐǑ]ǙśƛËŮHďDåũìl ĥ V L Y l Ĺ g G \ N T Ǵ ­ N dz�'y#5����.� �β \VDW^dz#5�.� H�ƚŮYNWťèNWFhdz×Ġń©ƕ]¼ōƼH£ĕ]ǂǮXCiǴ�� łƆƑXōƼNTµƛƥī\fiƞĠřeµƛǘ¿]ÂĘ^dzĖŅ]ǙËŮl�ĚYNTŮlj×ĠX�ƬŽ\ŷDgjWITġšXChdzL]ġšl×ĠHâǩYǁdžMjWDTǙśƛËŮ\ÀcWǕĜXITLY^dz£ĕ]ŮljĩƜ]³ǒ\ƣHiŀž[ƅ

Inte

nsity

(a.u

.)

2624222018161412108642θ / º (λ = 0.6 Å)

002

002

004

101103

110

112 105006

114200

013103

110011

101004

112 006015

105

114

020 022

La2LiHO3 (Immm)

LaSrLiH2O2 (I4/mmm)

La0.6Sr1.4LiH2.4O1.6 (I4/mmm)

Sr2LiH3O(I4/mmm)

: Unknown: SrLiH3

La1.5Sr0.5LiH1.5O2.5 (I4/mmm)

La2LiHO3 (x = 0) LaSrLiH2O2 (x = 1.0) Sr2LiH3O (x = 2.0)

H-

O

La

Li H-

O

Li

La/Sr Sr

H-/O

H-

Li

Page 3: ( J GH 0 /2= 'E :/2 ? ?F/2 - KAKEN...X^300 ºCX > d ðD ë q ñ 9 # )1 òH gj T ñä3(c) ò ô H Uµ }\¾ NT ÓÅ ' y#5 . β ] ë q] g ±÷ lä * \ P ô ' #5 . X^ ; X ðD ë q 9 #

ƶXCiǴ�

ä ��×ĠNTǙśƛËŮ]Ƃä�

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]or�ăǫű]ŧб÷ĝlƉPǴ����ÚŀǛHðEdz����] ŕµaT^�ŕµĤįHÓƩ\[iLYXăǫű^Ù�NdzŢĝ²q��u�^¯ŦNTǴNGN?����HŌöºl�ൎ\ÏŀNT#5��.� X^dz�5 ǪãŚ�X^ �;� X¾ƺÑĜHŶOiTcdz�ǢŧĐl ����;� YNTǴ�� ����H ŕµƷÄǘ¿NT �'#5�.�� �

] �.�� č Ǭ � \ Ŕ Ĭ l ă · N T�'��α#5��α�.���α � X^dzŔĬ]ă·\fhăǫűHÙ�NTHdzŢĝ²q��u�\ŀĞ[ñË^ǁcgj[GUTDZä �(�DzǴăǫű]Ù�^ŌöǠ\����lă·NT����ǓÅƞĠ\FDWdØő\ƸŨMjdzƞĠ �'���#5���.���� ��β������X^ 300 ºC XľdǰDăǫűDZ����9�����#�)1��DzHėgjTDZä 3(c)DzǴ�� ����H�ൎ\¾ĊNT����ǓÅƂ �'y#5����.� �β ��������� ���������]ăǫű]ŧб÷ĝlä �*�\ƉPǴƞĠ�'��#5����.� �� ���������X^ ����;� XǰDăǫű ���9�����#�)1��lƉNTHdz¤]åũ°YŻ[hdzµƛƥī\fiăǫűÙ�]ÊŊ^óIJŲjQdzŢĝ²q��u�]´\dŀĞ[ĉ^ǁcgj[GUTǴLj^dz��'y#5����.� �β H�ƚŮlÚbdzÎƂXėgj[GUTLY\NJáPiǴ�

ä ��×ĠNTǙśƛËŮ]or�ăǫű]ŧб÷ĝdz�'���'���#5��.���� ����9����������dz�(���'��α#5��α�.���α ���α �����������dz�)�� �'��β#5��β�.���β �� �β� �� �� ��� dz �*���'y#5����.� �β ��������� �����������ǺǴ�[żƳDŽıƕ�AøªżƳBDZƻ 5 ©Dz =� ŇĆğŠdzĄʼnŰÞdzčąǧƓdzƯǚ�

ŕdz���.�� ê����ÚŀǙËŮ]ǰç×ĠYor�ăǫŮĝdzƔ �� ày��}

Sr2LiHO2

La1-αSr1+αLiH2-αO2

�������

���� ��

�����

(Immm)�

(I4/mmm)�

H-�

Sr2LiH3O La2LiH5O

La2LiHO3

La2-xSr xLiH1+xO3-x

La2 LiH

5-2z O1+z

LaySr2-yLiH3+yO

La1+βSr1-βLiH2+βO2

LaSrLiH2O2

����H-���

-7.0

-6.5

-6.0

-5.5

-5.0

-4.5

-4.0

log / S

·cm-1

2.22.12.01.91.81.7103T-1 / K-1

La2LiHO3 (x = 0)LaSrLiH2O2 (x = 1)Sr2LiH3O (x = 2)

-7.0

-6.5

-6.0

-5.5

-5.0

-4.5

-4.0

log / S

·cm-1

2.001.951.901.851.801.751.70103T-1 / K-1

LaSrLiH2O2 = 0.2 = 0.4

(a)

(b)

-6.5

-6.0

-5.5

-5.0

-4.5

-4.0

-3.5

-3.0log

/ S·cm

-1

2.12.01.91.81.7103T-1 / K-1

LaSrLiH2O2 = 0.4

-6.5

-6.0

-5.5

-5.0

-4.5

-4.0

-3.5

-3.0

log / S

·cm-1

2.22.12.01.91.81.7103T-1 / K-1

Sr2LiH3Oy = 0.3y = 0.4y = 0.6

(c)

(d)

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