Stage Transitions in Graphite Intercalation ... - ACS Publications

Jul 17, 2019 - two SPI-1 and SPI-3, according to the manufacturer's specifications ... Acquired with the SPI-1 HOPG sample. ..... Science 2004, 306, 6...
0 downloads 0 Views 817KB Size
Subscriber access provided by UNIV OF SOUTHERN INDIANA

C: Physical Processes in Nanomaterials and Nanostructures

The Stage Transitions in Graphite Intercalation Compounds. The Role of the Graphite Structure Ayrat M. Dimiev, Ksenia Shukhina, Natnael Behabtu, Matteo Pasquali, and James M. Tour J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/acs.jpcc.9b06726 • Publication Date (Web): 17 Jul 2019 Downloaded from pubs.acs.org on July 20, 2019

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 27 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

The Journal of Physical Chemistry

The Stage Transitions in Graphite Intercalation Compounds. The Role of the Graphite Structure Ayrat M. Dimiev,a* Ksenia Shukhina,a Natnael Behabtu,b Matteo Pasqualib,c and James M. Tourc* a

Laboratory for Advanced Carbon Nanomaterials, Kazan Federal University, Kremlyovskaya str. 18, Kazan 420008, Russian Federation; bDepartment of Chemical and Biomolecular Engineering, Rice University; cDepartments of Chemistry and Materials Science and

NanoEngineering, Smalley-Curl Institute, Rice University, 6100 Main Street, Houston, Texas, 77005, USA &RUUHVSRQGLQJ DXWKRUV H PDLO $0'LPLHY#NSIX UX $ 0 'LPLHY WRXU#ULFH HGX - 0 7RXU

Abstract 'HVSLWH LQWHQVLYH DQG ORQJ ODVWLQJ UHVHDUFK RQ JUDSKLWH LQWHUFDODWLRQ FRPSRXQGV *,&

WKH

PHFKDQLVP RI WKH VWDJH WUDQVLWLRQV UHPDLQV REOLYLRXV 8VLQJ RSWLFDO DQG 5DPDQ PLFURVFRS\ ZH SHUIRUP GLUHFW UHDO WLPH PRQLWRULQJ RI VWDJH WUDQVLWLRQV LQ + 62 *,& PDGH IURP KLJKO\ RULHQWHG S\UROLWLF JUDSKLWH +23* :H REVHUYH WKDW VWDJH WUDQVLWLRQV LQ +23* EDVHG *,& RFFXU YHU\ GLIIHUHQWO\ IURP WKRVH LQ *,& PDGH IURP WKH QDWXUDO IODNH JUDSKLWH 'XULQJ WKH VWDJH WUDQVLWLRQ IRUPDWLRQ RI WKH VWDJH

WR VWDJH

SKDVH EHJLQV QHDUO\ VLPXOWDQHRXVO\ RYHU WKH HQWLUH JUDSKLWH

VXUIDFH WKDW LV H[SRVHG WR WKH PHGLD :H DWWULEXWH WKLV FRQFHUWHG WUDQVLWLRQ WR WKH PRYHPHQW RI WKH VPDOO LQWHUFDODQW SRUWLRQV WRZDUG WKH SRLQWV RI DWWUDFWLRQ WKXV JURZLQJ FRQWLQXRXV LVODQGV 'XULQJ WKH UHYHUVH SURFHVV WKH VWDJH

WR VWDJH

WUDQVLWLRQ EHJLQV VWULFWO\ IURP WKH HGJHV RI WKH JUDSKLWH

VDPSOH DQG SURSDJDWHV WRZDUG WKH FHQWHU RI WKH JUDSKLWH VDPSOH 7KH GHLQWHUFDODWLRQ IURQW LV

ACS Paragon Plus Environment

The Journal of Physical Chemistry 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 2 of 27

GLVFRQWLQXRXV WKH VHOHFWHG PLFURPHWHU VL]HG GRPDLQV RI WKH JUDSKLWH VXUIDFH GHLQWHUFDODWH SUHIHUHQWLDOO\ WR UHOHDVH WKH VWUDLQ WKDW KDG EHHQ LQGXFHG E\ WKH LQWHUFDODWLRQ 7KH LQWHUFDODQW G\QDPLFV LQ WKH ' JUDSKLWH JDOOHULHV RFFXUULQJ DW WKH VSHHG !

—P V KDV IDVW NLQHWLFV 7KH

LQLWLDO LQWHUFDODWLRQ SURFHVV LV GLIIHUHQW IURP WKH UHVW RI WKH UHLQWHUFDODWLRQ F\FOHV 7KH GLIIHUHQFH LQ WKH PHFKDQLVPV RI WKH VWDJH WUDQVLWLRQV LQ QDWXUDO IODNH JUDSKLWH EDVHG *,&V DQG LQ WKH +23* EDVHG *,&V H[HPSOLILHV WKH UROH RI WKH JUDSKLWH VWUXFWXUH IRU WKH LQWHUFDODQW G\QDPLFV LQ ' JUDSKLWH JDOOHULHV

Keywords JUDSKLWH LQWHUFDODWLRQ FRPSRXQGV *,& JUDSKLWH RSWLFDO VSHFWURVFRS\ 5DPDQ VSHFWURVFRS\

1. Introduction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

1XPHURXV *,&V ZLWK GLIIHUHQW

LQWHUFDODQWV KDYH EHHQ V\QWKHVL]HG DQG UHSRUWHG ,Q UHFHQW \HDUV DIWHU GLVFRYHULQJ WKH IDVFLQDWLQJ SURSHUWLHV RI JUDSKHQH

DQG WKH KLJKHU WHPSHUDWXUH VXSHUFRQGXFWLYLW\ LQ &D&

*,&V VWDUWHG

JDLQLQJ UHQHZHG LQWHUHVW 7KHUH DUH VHYHUDO UHDVRQV WR SD\ FORVH DWWHQWLRQ WR *,&V )LUVW *,& FDQ EH FRQVLGHUHG DV VWDFNV RI GRSHG JUDSKHQH ZKLFK FDQ EH HDVLO\ SUHSDUHG E\ IXOO\ UHYHUVLEOH UHDFWLRQV WKH GRSLQJ OHYHO FDQ EH HDVLO\ FRQWUROOHG E\ WKH UHDFWLRQ FRQGLWLRQV 6HFRQGO\

ACS Paragon Plus Environment

Page 3 of 27 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

The Journal of Physical Chemistry

LQWHUFDODWLRQ ZHDNHQV WKH DGKHVLYH IRUFHV EHWZHHQ WKH DGMDFHQW JUDSKHQH OD\HUV WKXV *,&V VHUYH DV SUHFXUVRUV IRU REWDLQLQJ VLQJOH OD\HU JUDSKHQH DQG JUDSKHQH QDQRSODWHOHWV via OLTXLG SKDVH H[IROLDWLRQ

7KLUG *,&V VHUYH DV LPSRUWDQW DQG XQDYRLGDEOH LQWHUPHGLDWHV HQ URXWH WR FRYDOHQW

IXQFWLRQDOL]DWLRQ RI JUDSKHQH GXH WR WKH FKDUJHG FRQGLWLRQ RI FDUERQ DWRPV 7KXV WKH R[R IXQFWLRQDOL]HG GHULYDWLYHV ZHUH REWDLQHG via + 62 *,& JUDSKHQHV ZHUH REWDLQHG via . *,&

DQG WKH DON\O DQG DU\O IXQFWLRQDOL]HG

)LQDOO\ DQG PRVW LPSRUWDQWO\ /L LRQ EDWWHU\ RSHUDWLRQ LV

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

VWDJH

VWDJH

*,&V UHVSHFWLYHO\ 'HVSLWH WKH HQRUPRXV UHVHDUFK

DWWHQWLRQ WKDW KDV EHHQ JLYHQ WR *,&V IXQGDPHQWDO TXHVWLRQV UHPDLQ UHJDUGLQJ WKH PHFKDQLVP RI WKH VWDJH WUDQVLWLRQV i.e KRZ GR *,&V RI GLIIHUHQW VWDJHV WUDQVIRUP LQWR HDFK RWKHU ,W LV SODXVLEOH WKDW LQWHUFDODWLRQ FDQ RFFXU RQO\ IURP WKH HGJHV RI JUDSKLWH VDPSOH 6XEVHTXHQWO\ WKH LQWHUFDODWLRQ IURQW VKRXOG SURSDJDWH IURP WKH HGJH RI WKH JUDSKLWH VDPSOH WRZDUG LWV FHQWHU 6RPH HDUO\ H[SHULPHQWV RQ HOHFWURFKHPLFDO LQWHUFDODWLRQ RI WKH KLJKO\ RULHQWHG S\UROLWLF JUDSKLWH +23* E\ + 62 SHUIRUPHG RQ WKH PDFURVFRSLF OHYHO VXJJHVW VXFK D PHFKDQLVP 7KLV VFHQDULR ZDV HYHQ H[WUDSRODWHG WR SURSRVH WKH VKULQNLQJ DQQXOL LQWHUFDODWLRQ PRGHO DQG WR HPSOR\ LW WR LQWHUSUHW SHUIRUPDQFH RI /L LRQ EDWWHULHV

$W WKH VDPH WLPH RWKHU VWXGLHV UHSRUWHG

REVHUYDWLRQV ZKLFK FDQ EH LQWHUSUHWHG DV LQWHUFDODWLRQ IURP WKH F IDFH 7KXV (NOXQG et al GLVFRYHUHG WKDW WKH VXUIDFH RI +23* ZKLFK ZDV LQ FRQWDFW ZLWK WKH DFLG UDSLGO\ FKDQJHG WKH VWDJH

ACS Paragon Plus Environment

The Journal of Physical Chemistry 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

LQGH[ WR n-1 MXVW DIWHU WKH EXON VDPSOH UHDFKHG VWDJH n

Page 4 of 27

7R H[SODLQ WKHVH REVHUYDWLRQV (NOXQG

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

WR VWDJH

WUDQVLWLRQ DQG YLFH YHUVD ,Q VXFK WUDQVLWLRQV WKH ILOOHG JUDSKHQH JDOOHULHV QHHG

WR EH HYDFXDWHG DQG WKH HPSW\ RQHV WR EH ILOOHG 6XFK D VFHQDULR VHHPV YHU\ XQOLNHO\ DQG LW LV QRW VXSSRUWHG E\ H[SHULPHQWDO REVHUYDWLRQV 7R H[SODLQ VXFK WUDQVLWLRQV 'DXPDV DQG +HUROG SURSRVHG LQ

WKH *,& VWUXFWXUDO PRGHO

ZKHUH *,&V ZLWK VWDJH

DQG KLJKHU GR QRW FRPSULVH IXOO\

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

ACS Paragon Plus Environment

Page 5 of 27 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

The Journal of Physical Chemistry

QHYHU GHWHFWHG DQG REVHUYHG H[SHULPHQWDOO\ 7KH DFWXDO PHFKDQLVP RI VWDJH WUDQVLWLRQV RQ WKH PLFUR OHYHO UHPDLQV P\VWHULRXV 0DQ\ VWDJH

DQG VWDJH

*,& LV GHHS EOXH DQG VWDJH

*,&V DUH FRORUHG )RU H[DPSOH LQ UHIOHFWHG OLJKW VWDJH

+ 62

+ 62 *,& LV ZKLWH 7KH DUHDV RI WKH PL[HG VWDJH ZKHUH WKH WZR

SKDVHV RYHUODS KDYH YHU\ EULJKW GLVWLQFW FRORUV UDQJLQJ IURP SXUSOH WKURXJK \HOORZ

,Q RXU

SUHYLRXV VWXG\ RQ + 62 *,& PDGH IURP WKH QDWXUDO IODNH JUDSKLWH )* ZH XVHG WKLV SURSHUW\ WR PRQLWRU WKH VWDJH WUDQVLWLRQV LQ UHDO WLPH E\ RSWLFDO PLFURVFRS\ DQG ZH UHSRUWHG VHYHUDO LQWULJXLQJ PHFKDQLVWLF GHWDLOV

,Q SDUWLFXODU ZH REVHUYHG D UHODWLYHO\ EURDG UDLQERZ FRORUHG VWULSH

VHSDUDWLQJ WKH VKULQNLQJ EOXH FRORUHG VWDJH

DQG WKH JURZLQJ ZKLWH FRORUHG VWDJH

DUHDV GXULQJ

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

2. Results and Discussion 7R PRQLWRU WKH VWDJH WUDQVLWLRQV ZH XVHG D VLPSOH EXW HIILFLHQW H[SHULPHQWDO VHW XS ZKHUH WKH JUDSKLWH VDPSOH ZDV VDQGZLFKHG EHWZHHQ D PLFURVFRSH VOLGH DQG D FRYHUVOLS EHLQJ IXOO\ VXUURXQGHG E\ WKH LQWHUFDODWLQJ DFLG VROXWLRQ 7KH RSWLFDO LPDJHV DQG 5DPDQ VLJQDOV ZHUH DFTXLUHG IURP WKH EDVDO VXUIDFH RI WKH JUDSKLWH VDPSOH WKURXJK WKH FRYHUVOLS DQG WKH OD\HU RI WKH DFLG VROXWLRQ 7R LQLWLDWH WKH LQWHUFDODWLRQ D VDPSOH RI +23* ZDV VLPSO\ LPPHUVHG LQWR WKH + 62

ACS Paragon Plus Environment

The Journal of Physical Chemistry 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

1+

Page 6 of 27

6 2 VROXWLRQ 7R LQLWLDWH GHLQWHUFDODWLRQ WKH DFLG VROXWLRQ ZDV GLOXWHG ZLWK ZDWHU WR ORZHU

LWV UHG R[ SRWHQWLDO 2.1. Stage-2 to Stage-1 Transition (Intercalation) 'XULQJ WKH GLUHFW SURFHVV WKH FRORU FKDQJH OHW XV PRQLWRU RQO\ WKH ILQDO VWHS RI LQWHUFDODWLRQ L H FRQYHUVLRQ RI VWDJH

*,& WR VWDJH

*,& )LJXUH

7KH WUDQVIRUPDWLRQ EHJLQV ZLWK DSSHDUDQFH

RI WKH SXUSOH FRORU DOO RYHU WKH VXUIDFH LQ WKH IRUP RI VKDSHOHVV IX]]\ FORXGV )LJXUH E 7KH SXUSOH DQG UHG FRORUV DSSHDU LQ WKH UHJLRQV RI WKH PL[HG VWDJH ZKHUH VWDJH

RYHUODSV ZLWK VWDJH

:LWK WLPH VRPH RI WKH UHG FRORUHG LVODQGV DFTXLUH VKDUS ERXQGDULHV DQG WKH EOXH FRORUHG LVODQGV DSSHDU VLJQLI\LQJ IRUPDWLRQ RI WKH SXUH VWDJH

UHJLRQV )LJXUH F G

:LWK UHDFWLRQ

SURJUHVVLQJ UHG DQG EOXH FRORUHG UHJLRQV JURZ DQG ILQDOO\ WKH EOXH FRORU RFFXSLHV DOPRVW DOO WKH VXUIDFH )LJXUH H I

Figure 1 2SWLFDO PLFURJUDSKV VKRZLQJ WUDQVLWLRQ RI VWDJH OLJKW 7KH VWDJH

DUHDV DUH JUHHQLVK ZKLWH 7KH VWDJH

*,& WR VWDJH

+23* *,& 5HIOHFWHG

DUHDV DUH EOXH 7KH UHG FRORUHG DUHDV DUH

WKH PL[HG VWDJH 1RWH WKH JUHHQLVK WLQW RI JUDSKLWH VXUIDFH RQ SDQHOV D E LV WKH DUWLIDFW RI WKH

ACS Paragon Plus Environment

Page 7 of 27 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

The Journal of Physical Chemistry

GLJLWDO SURFHVVLQJ WKH DFWXDO FRORU LV DOPRVW ZKLWH 7KH ZKLWH VKDSHOHVV IHDWXUH RQ WKH ULJKW RI WKH PLFURJUDSKV LV DQ DLU EXEEOH $FTXLUHG ZLWK WKH 63,

+23* VDPSOH

,Q DGGLWLRQ WR WKH RSWLFDO LPDJHV WKH VWDJH WUDQVLWLRQ FDQ EH HIILFLHQWO\ PRQLWRUHG E\ 5DPDQ PLFURVFRS\ VLQFH WKH 5DPDQ VSHFWUD RI JUDSKLWH DUH YHU\ VHQVLWLYH WR LQWHUFDODWLRQ SDUWLFXODU VWDJH

DQG VWDJH

*,&V FDQ EH HDVLO\ DQG XQDPELJXRXVO\ LGHQWLILHG E\ WKHLU 5DPDQ

VSHFWUD :LWK LQWHUFDODWLRQ WKH * EDQG VKLIWV IURP DQG

FP IRU VWDJH

FP WKURXJK

FP IRU VWDJH

*,&

*,& 7KH XS VKLIW RFFXUV GXH WR WKH FKDUJLQJ JUDSKHQH OD\HUV ZLWK

LQWHUFDODQW PROHFXOHV $OVR IRU VWDJH

*,& WKH ' EDQG LV IXOO\ VXSSUHVVHG GXH WR WKH 3DXOL

EORFNLQJ IRU ODVHU HQHUJLHV EHORZ WKH GRSLQJ OHYHO

7KH 5DPDQ VSHFWUD DFTXLUHG IURP WKH ZKLWH

FRORUHG DQG EOXH FRORUHG DUHDV FRQILUP WKH SUHVHQFH RI VWDJH )LJXUH 6

,Q

DQG VWDJH

*,& UHVSHFWLYHO\

7KH VSHFWUD DFTXLUHG IURP WKH UHG FRORUHG DUHDV FRQILUP WKH SUHVHQFH RI WKH PL[HG

VWDJH *,& LQ IXOO DFFRUGDQFH ZLWK RXU SUHYLRXVO\ SXEOLVKHG GDWD IRU )* EDVHG + 62 *,& 7KH REVHUYHG FRORUHG LQWHUFDODWLRQ SDWWHUQ )LJXUH

VXJJHVWV WKDW WKH VWDJH

WR VWDJH

WUDQVLWLRQ EHJLQV QHDUO\ VLPXOWDQHRXVO\ DOO RYHU WKH YLVLEOH JUDSKLWH VXUIDFH EXW GRHV QRW SURFHHG VWULFWO\ IURP WKH HGJHV DV RQH PLJKW H[SHFW 7KLV REVHUYDWLRQ LV VLPLODU WR ZKDW ZDV REVHUYHG E\ (NOXQG et al GXULQJ WKH HOHFWURFKHPLFDO LQWHUFDODWLRQ RI +23* LQ VXOIXULF DFLG

,Q WKDW ZRUN

SHUIRUPHG RQ WKH PDFURVFRSLF OHYHO (NOXQG VXJJHVWHG WKDW VXOIXULF DFLG PROHFXOHV PLJKW LQWHUFDODWH WKURXJK WKH PLFURFUDFNV RU VWHSV RQ WKH JUDSKLWH VXUIDFH

2XU REVHUYDWLRQV VWURQJO\

VXJJHVW DJDLQVW VXFK VFHQDULR )LUVW WKH SXUSOH FORXGV DSSHDU UDQGRPO\ HYHU\ZKHUH )LJXUH E WKH\ GR QRW IROORZ DQ\ SDWWHUQ WKDW PLJKW EH LQWHUSUHWHG DV FUDFNV RU VWHSV 6HFRQGO\ WKH ODWHUDO GHQVLW\ RI WKHVH SXUSOH FORXGV LV WRR KLJK WR EH LQWHUSUHWHG DV WKH YDFDQF\ GHIHFWV %\ GHILQLWLRQ +23* FDQQRW FRQWDLQ WKDW PDQ\ YDFDQF\ GHIHFWV ZLWK D VL]H WKDW SHUPLWV VXOIXULF DFLG PROHFXOHV

ACS Paragon Plus Environment

The Journal of Physical Chemistry 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

WR SHUPHDWH )LJXUH E 7KXV WKH REVHUYHG VWDJH

WR VWDJH

Page 8 of 27

WUDQVLWLRQ VFHQDULR PXVW KDYH D

GLIIHUHQW H[SODQDWLRQ 7KH JURZWK RI WKH IX]]\ FORXGV )LJXUH E F PXVW EH DVVRFLDWHG ZLWK WKH VPDOO LQWHUFDODQW SRUWLRQV WKH 'DXPDV +HUROG GRPDLQV VOLGLQJ WRZDUG WKH SRLQWV RI JURZWK DQG EXLOGLQJ XS ODUJH FRQWLQXRXV LVODQGV DV ZH SUHVHQW VFKHPDWLFDOO\ LQ )LJXUH

6LQFH WKH SKRWRJUDSKV LQ )LJXUH

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et al DV WKH GHIHFW WKURXJK SHQHWUDWLRQ RI DFLG PROHFXOHV WKURXJK XSSHU JUDSKHQH OD\HUV

Figure 2 7KH VFKHPDWLF VKRZLQJ WKH SURFHVV RI VWDJH

WR VWDJH

WUDQVLWLRQ GXULQJ WKH RULJLQDO

LQWHUFDODWLRQ 7KH EURDG VWULSH RQ WKH WRS UHSUHVHQWV WKH FRORU KRZ WKH JUDSKLWH VXUIDFH DSSHDUV LQ WKH PLFURVFRSH LQ UHIOHFWHG OLJKW 7KH VWUXFWXUH EHORZ UHSUHVHQWV WKH *,& VWUXFWXUH LQ WKH JURZLQJ SXUSOH FRORUHG DUHDV 7KH UHG DUURZV VKRZ WKH GLUHFWLRQ RI WKH VPDOO LQWHUFDODQW SRUWLRQV WRZDUG WKH JURZLQJ FRQWLQXRXV LVODQG LQ WKH PLGGOH

ACS Paragon Plus Environment

Page 9 of 27 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

The Journal of Physical Chemistry

,W KDV EHHQ HVWDEOLVKHG WKDW WKH JUDSKHQH OD\HU ZKLFK LV LQ FRQWDFW ZLWK LQWHUFDODQW HIIHFWLYHO\ VFUHHQV WKH LQQHU OD\HUV IURP WKH LQWHUFDODQW WKHUHE\ LQKLELWLQJ ORQJ UDQJH HOHFWURVWDWLF LQWHUDFWLRQV LQ *,&V

6XEVHTXHQWO\ ZKLOH LQWHUFDODQW FDQ LQGHHG HQWHU WKH VDPSOH RQO\ IURP

HGJHV LQWHUFDODWLRQ VKRXOG RFFXU RQO\ OD\HU E\ OD\HU VWDUWLQJ IURP WKH RXWHUPRVW OD\HU H[SRVHG WR LQWHUFDODWLQJ PHGLD :LWK UHVSHFW WR WKH VWDJH

WR VWDJH

WUDQVLWLRQ WKLV SULQFLSOH LV LPSOHPHQWHG

LQ WKH ZD\ WKDW VPDOO LQWHUFDODQW SRUWLRQV VWDUW GHQVLI\LQJ DQG EXLOGLQJ XS FRQWLQXRXV LVODQGV LQ WKH ILUVW LQWHUOD\HU JDOOHU\ EHWZHHQ WKH RXWHUPRVW DQG WKH VHFRQG JUDSKHQH OD\HUV ILUVW 7KLV LV H[DFWO\ ZKDW ZH REVHUYH LQ )LJXUH

2.2. Stage-1 to Stage-2 Transition (Deintercalation) 7R LQLWLDWH GHLQWHUFDODWLRQ D GURS RI ZDWHU ZDV SODFHG RQ WKH PLFURVFRSH VOLGH DW WKH HGJH RI WKH FRYHUVOLS WR GLOXWH WKH DFLG VROXWLRQ 6LQFH WKH DFLG FRPHV LQWR FRQWDFW ZLWK WKH DGGHG ZDWHU RQO\ DORQJ WKH WKLQ FURVV VHFWLRQ DW WKH HGJH RI WKH FRYHUVOLS WKH GLOXWLRQ RFFXUV via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

9LGHR 6

7KH ZKLWH FRORUHG IURQW GLUHFWLRQDOO\ SURSDJDWHV WKURXJK WKH RULJLQDOO\ EOXH

FRORUHG JUDSKLWH VXUIDFH 7KHUH LV D UHODWLYHO\ QDUURZ UDLQERZ FRORUHG VWULSH EHWZHHQ WKH WZR

ACS Paragon Plus Environment

The Journal of Physical Chemistry 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

SKDVHV 0RUH GHWDLOV RI WKLV WUDQVLWLRQ DUH YLVLEOH DW KLJKHU PDJQLILFDWLRQ )LJXUH

Page 10 of 27

9LGHR 6

7KH

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

$SSDUHQWO\ WKH GLIIHUHQFH LQ WKH JUDSKLWH ODWWLFH

VWUXFWXUH LV UHVSRQVLEOH IRU WKH GLIIHUHQFH LQ WKH VWDJH WUDQVLWLRQ SDWWHUQ

Figure 3 2SWLFDO PLFURJUDSKV VKRZLQJ VWDJH

WR VWDJH

WUDQVLWLRQ LQ +23* + 62 *,& 7KH

VWDJH WUDQVLWLRQ IURQW SURSDJDWHV IURP WKH OHIW XSSHU FRUQHU WKURXJK WKH ULJKW ERWWRP 7KH VWDJH

ACS Paragon Plus Environment

Page 11 of 27 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

The Journal of Physical Chemistry

DUHD LV GHHS EOXH WKH VWDJH ZLWK WKH 63,

DUHD LV ZKLWH WKH PL[HG VWDJH DUHDV DUH UDLQERZ FRORUHG $FTXLUHG

+23* VDPSOH

7KH 5DPDQ VSHFWUD DFTXLUHG IURP RQH VWDWLF SRLQW RQ WKH JUDSKLWH VXUIDFH ZKHQ WKH WUDQVLWLRQ IURQW SDVVHV WKURXJK LW GHPRQVWUDWH JUDGXDO WUDQVIRUPDWLRQ RI VWDJH *,& WKURXJK WKH PL[HG VWDJH FRQGLWLRQ )LJXUH

1RWH WKH * EDQG RI WKH VWDJH

VHOHFWLYHO\ HQKDQFHG E\ WKH JUHHQ ODVHU )LJXUH D ZKLOH WKH * EDQG IRU VWDJH WKH UHG ODVHU )LJXUH E

SKDVH LV

LV HQKDQFHG E\

7KLV RFFXUV GXH WR WKH HOLPLQDWLRQ RI GHVWUXFWLYH LQWHUIHUHQFH DW WKH

ODVHU HQHUJLHV LQ WKH YLFLQLW\ RI WKH GRXEOH )HUPL HQHUJ\ DQG * SHDNV )LJXUH

*,& WR VWDJH

7KHUHIRUH WKH UHODWLYH LQWHQVLWLHV RI *

FDQQRW EH XVHG WR DVVHVV WKH DFWXDO UDWLR RI WKH VWDJH

DQG VWDJH

SKDVHV

1HYHUWKHOHVV WKH VSHFWUD FOHDUO\ GHPRQVWUDWH KRZ WKH ODWWHU JURZV DW WKH H[SHQVH RI WKH IRUPHU ,QWHUHVWLQJO\ LQ WKLV ZRUN ZH GLG QRW REVHUYH ULVLQJ RI WKH KLJK DQG EURDG ' EDQG GXULQJ WKH VWDJH WUDQVLWLRQ ZKLFK ZDV UHJLVWHUHG GXULQJ WKH VWDJH

WR VWDJH

WUDQVLWLRQ ZLWK )* EDVHG *,&

7KLV

LV DQRWKHU SURIRXQG GLIIHUHQFH EHWZHHQ WKH VWDJH WUDQVLWLRQV LQ WKH *,& PDGH IURP +23* DQG )*

ACS Paragon Plus Environment

The Journal of Physical Chemistry 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Figure 4 5DPDQ VSHFWUD UHSUHVHQWLQJ WKH VWDJH D $FTXLUHG ZLWK WKH QXPEHUV

WR VWDJH

WUDQVLWLRQ LQ WKH +23* + 62 *,&

QP H[FLWDWLRQ ODVHU E $FTXLUHG ZLWK WKH

QP H[FLWDWLRQ ODVHU 7KH

UHSUHVHQW WKH IRXU VSHFWUD DFTXLUHG FRQVHFXWLYHO\ IURP WKH VDPH VWDWLF SRLQW RQ

WKH JUDSKLWH VXUIDFH ZKLOH WKH WUDQVLWLRQ IURQW SDVVHV WKURXJK LW * EDQG IRU VWDJH

Page 12 of 27

DQG VWDJH

DQG *

UHSUHVHQW WKH *

SKDVHV UHVSHFWLYHO\ 7KH VSHFWUD DUH QRW QRUPDOL]HG 7KH VDPH

DFTXLVLWLRQ WLPH ZDV XVHG IRU DOO WKH HLJKW VSHFWUD

,Q RXU HDUOLHU ZRUN

ZH FRXOG QRW DFTXLUH 5DPDQ VSHFWUD VLPXOWDQHRXVO\ ZLWK UHFRUGLQJ

RSWLFDO LPDJHV WKH VWDJH WUDQVLWLRQ LV YHU\ TXLFN DQG DFTXLVLWLRQ RI 5DPDQ VSHFWUD LV VLJQLILFDQWO\ VORZHU +HUH ZH VROYHG WKLV SUREOHP ZLWK WKH KHOS RI QHZ HTXLSPHQW VHH H[SHULPHQWDO SDUW IRU GHWDLOV WKDW DOORZV XV WR SURYLGH VLJQLILFDQW HYLGHQFH IRU WKH VWURQJ FRUUHODWLRQ EHWZHHQ WKH RSWLFDO

ACS Paragon Plus Environment

Page 13 of 27 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

The Journal of Physical Chemistry

LPDJHV DQG WKH 5DPDQ VSHFWUD 7KH PRQRFKURPDWLF RSWLFDO LPDJHV 5D\OHLJK VFDWWHULQJ ZHUH UHFRUGHG VLPXOWDQHRXVO\ ZLWK WKH XOWUD IDVW 5DPDQ PDSSLQJ UHFRUGHG DW WKH ZDYHOHQJWK WKH ILQJHUSULQW RI VWDJH

FP

*,& )LUVW ZH SUHVHQW WKH WKUHH LPDJHV FRQVHFXWLYHO\

DFTXLUHG IURP WKH VDPH DUHD RI WKH JUDSKLWH VXUIDFH LQ FRQGLWLRQ RI WKH IUR]HQ VWDJH WUDQVLWLRQ WR VKRZ WKDW WKH PRQRFKURPDWLF RSWLFDO LPDJH WKH 5DPDQ PDS DQG WKH IXOO FRORU RSWLFDO LPDJH IXOO\ FRLQFLGH )LJXUH 6 VLJQDO DW WKH

2Q WKH 5DPDQ PDSV WKH EOXH FRORUHG DUHD DSSHDUV EULJKW VLQFH WKH

FP ZDYHOHQJWK ZDV GHWHFWHG DQG WKH FRORUHG GRPDLQV DSSHDU GDUN VLQFH WKH\

GR QRW FRQWDLQ VWDJH

SKDVH 1RWH WKH DUHDV ZKLFK DSSHDUHG RQ WKH IXOO FRORU RSWLFDO PLFURJUDSKV

DV SXUSOH FRORUHG RQ WKH UHVSHFWLYH 5DPDQ PDSV ORRN EULJKW ZLWK DOPRVW QR FRQWUDVW WR WKH SXUH VWDJH

DUHDV 7KLV REVHUYDWLRQ LV LQ DFFRUG ZLWK )LJXUH D DQG ZLWK RXU HDUOLHU REVHUYDWLRQV

SXUSOH DUHDV WKH FRQWHQW RI WKH VWDJH

LQ

SKDVH LV WRR ORZ WR PDNH D QRWDEOH LPSDFW RQ WKH 5DPDQ

VSHFWUD DFTXLUHG ZLWK WKH JUHHQ H[FLWDWLRQ ODVHU $V WKH QH[W VWHS ZH UHFRUGHG WKH VLJQDOV IURP WKH WZR FKDQQHOV VLPXOWDQHRXVO\ GXULQJ WKH DFWXDO IDVW SURSDJDWLQJ VWDJH WUDQVLWLRQ )LJXUH

7KH

PRQRFKURPDWLF RSWLFDO LPDJHV )LJXUH D F FRLQFLGH ZLWK WKH FRUUHVSRQGLQJ 5DPDQ PDSV )LJXUH G I $JDLQ RQ WKH 5DPDQ PDSV WKH RULJLQDO VWDJH DSSHDU GDUN VLQFH WKH\ FRQWDLQ OHVV RU QR VWDJH REVHUYHG GXULQJ WKH WUDQVLWLRQ )LJXUH

DUHD DSSHDUV EULJKW DQG WKH OLW GRPDLQV

SKDVH 7KLV FRQILUPV WKDW WKH FRORUHG OLW GRPDLQV

DUH LQGHHG WKH DUHDV ZKHUH VWDJH

LV WUDQVLWLRQHG WR VWDJH

$OVR WKH H[SHULPHQW GHPRQVWUDWHV WKDW WKH 5DPDQ VLJQDO FKDQJHV VLPXOWDQHRXVO\ DQG DV TXLFNO\ DV WKH RSWLFDO LPDJH

ACS Paragon Plus Environment

The Journal of Physical Chemistry 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Figure 5 7KH VWDJH

WR VWDJH

WUDQVLWLRQ UHFRUGHG VLPXOWDQHRXVO\ IURP WKH WZR LQGHSHQGHQW

FKDQQHOV PRQRFKURPDWLF RSWLFDO LPDJHV D F

DQG WKH XOWUD IDVW 5DPDQ PDSSLQJ G I

5DPDQ PDSSLQJ ZDV VHW RQ GHWHFWLQJ WKH VLJQDO DW WKH ZDYHOHQJWK DSSHDU EULJKW DQG WKH VWDJH

Page 14 of 27

DUHDV DSSHDU GDUN G I 7KH

7KH WLPH EHWZHHQ WKH LPDJHV D G DQG E H LV

FP

WKH VWDJH

7KH DUHDV

QP ODVHU ZDV XVHG IRU WKH H[FLWDWLRQ

V EHWZHHQ WKH LPDJHV E H DQG F I LV

V

$FTXLUHG ZLWK WKH =