2010B1800㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 BL46XU◳ X ⥺ග㟁Ꮚศගἲ䜢⏝䛔䛯 Li/Na 䜲䜸䞁㟁ụ⏝㟁ᴟᮦᩱ䛾䝞䝹䜽ᵓ㐀䛸⾲㠃ᵓ㐀䛻㛵䛩䜛◊✲Studies on Bulk and Surface Stuctures of Electrodes for Advanced Li /Na-Ions Rechargeable Batteries by Hard X-Ray Photoemission
Spectroscopy㥖ሙ ៅ୍ a, ⸭ෆ ┤᫂ a, Ꮮ ⌋Ọ b, 㝜ᆅ ᏹ b, ྜྷᕝ Ṋᚨ a, ▼ᕝ ᚭ a
Shinichi Komabaa, Naoaki Yabuuchia, Jin-Young Sonb , Hiroshi Ojib, Takenori Yoshikawaa, Toru Ishikawaaaᮾி⌮⛉኱Ꮫ, b㻔㈈㻕㧗㍤ᗘග⛉Ꮫ◊✲䝉䞁䝍䞊
㻌 aTokyo University of Science, bJASRIࣜࢳ࣒࢘㟁ụ⏝ࡢḟୡ௦㟁ᴟᮦᩱ࡜ࡋ࡚㟁Ẽ⮬ື㌴⏝㟁ụ࡞࡝኱ᆺ⏝㏵ࢆᚿྥࡋࡓᆅẆ୰ࡢ㈨※㔞ࡀ㇏ᐩ࡞ Mn ࡸ Si ࢆ࣮࣋ࢫ࡜ࡋࡓ㟁ᴟᮦᩱࡀὀ┠ࡉࢀ࡚࠸ࡿࠋᙜヱㄢ㢟࡟࠾࠸࡚ࡣ㧗ᐜ㔞
Li2MnO3-LiCo1/3Ni1/3Mn1/3O2 ⣔ṇᴟᮦᩱࠊࡲࡓࠊ㧗ᐜ㔞 Si ⣔㈇ᴟᮦᩱ࡟ࡘ࠸࡚ࡢ཯ᛂᶵᵓࡢゎ᫂ࢆ┠ⓗ࡜ࡋࠊ◳ X ⥺ග㟁Ꮚศගἲ㻔HAXPES㻕ࢆ⏝࠸ࡓ ᐃࢆ⾜ࡗࡓࠋࡲࡓࠊḟୡ௦ᆺ㟁ụ࡜ࡋ࡚࣏ࢫࢺࣜࢳ࣒࢘࢖࢜ࣥ㟁ụࢆᚿྥࡋࡓ Na ࢖࢜ࣥ㟁ụ⏝ࡢ㟁ᴟᮦᩱ࡟㛵ࡍࡿ ᐃࡶ⾜ࡗࡓࠋ㏻ᖖࡢ
㌾ X ⥺ග㟁Ꮚศගἲ䠄SX-PES䠅࡛ࡣ ᐃ୙ྍ⬟࡛࠶ࡗࡓᮦᩱࣂࣝࢡ࠿ࡽࡢග㟁Ꮚ᳨ฟ࡟ᡂຌࡋࠊ
HAXPES ࡀ㟁ụᮦᩱࡢゎᯒ࡟࠾࠸࡚㠀ᖖ࡟᭷⏝࡞ᡭἲ࡜ᡂࡾᚓࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ࣮࣮࢟࣡ࢻ㸸 Li ࢖࢜ࣥ஧ḟ㟁ụࠊNa ࢖࢜ࣥ஧ḟ㟁ụࠊ◳ X ⥺ග㟁Ꮚศගἲ⫼ᬒ࡜◊✲┠ⓗ㸸㏆ᖺࠊ ᬮ໬ࢆࡣࡌࡵ࡜ࡋࡓᆅ⌫⎔ቃ࡟࠾ࡅࡿㅖၥ㢟ࡢゎỴ⟇࡜ࡋ࡚ࠊపⅣ⣲໬♫఍࡬࡜ྥࡅࡓྲྀࡾ⤌ࡳࡀୡ⏺ྛᅜ࡛㐍ࢇ࡛࠸ࡿࠋ⌧ᅾࠊࡑࡢ୍Ṍ࡜ࡋ࡚㟁Ẽ⮬ື㌴ࡀᕷሙ࡟ᢞධࡉࢀࡿࡲ࡛࡟࡞ࡗ࡚࠸ࡿࡶࡢࡢࠊࡑࡢ㟁※࡜ࡋ࡚⏝࠸ࡽࢀ࡚࠸ࡿ Li ࢖࢜ࣥ㟁ụࡣᚑ᮶ࡼࡾࡶ኱ᆺ࡛࠶ࡾࠊࡉࡽ࡞ࡿ㧗ᛶ⬟໬࡜పࢥࢫࢺ໬ࡀᛴົ࡛࠶ࡿࠋᡃࠎࡣ㈨※㔞ࡀ㇏ᐩ࡞ Mn ࡜ Si ࢆ࣮࣋ࢫ࡜ࡋࡓṇ
ᴟ࣭㈇ᴟᮦᩱ࡟╔┠ࡋ࡚⣔⤫ⓗ࡞◊✲ࢆ㐍ࡵ࡚ࡁ࡚࠸ࡿࠋࡲࡓࠊḟୡ௦ᆺࠕ࣏ࢫࢺ Li 㟁ụࠖ࡟㛵ࡍࡿ◊✲ࡶ㐍ࡵ࡚࠾ࡾࠊLi ࢆ඲ࡃ⏝࠸ࡎࠊࣞ࢔࣓ࢱࣝࣇ࣮ࣜᵓᡂࢆᐇ⌧ࡍࡿࠕNa ࢖࢜ࣥ㟁ụࠖࡢ◊✲ࢆ⾜ࡗ࡚࠸ࡿࠋᮏㄢ㢟࡛ࡣࠊ㻔1㻕 ᪤Ꮡ Li 㟁ụࡢࡉࡽ࡞ࡿ㧗࢚ࢿࣝࢠ࣮ᐦᗘ໬ࢆ┠ᣦࡋࠊ᪂つ㟁ᴟᮦᩱࡢ཯ᛂᶵᵓࡢゎ᫂࡜㧗ᛶ⬟໬ࠊ㻔2㻕 Na 㟁ụࡢᐇ⌧࡟ྥࡅ࡚㔜せ࡞ㄢ㢟࡛࠶ࡿ㟁ᴟᮦᩱ⾲㠃࡟Ꮡᅾࡍࡿ≀㉁ࡢ㓟໬ᩘࡸศᩓ≧ែ࡟㛵ࡋ࡚ࠊ◳ X ⥺ග㟁Ꮚศගἲ㻔HAXPES㻕ࢆ⏝࠸᳨࡚ウ
ࡋࡓࠋLi ࡜ Na ⣔ࡒࢀࡒࢀ࡛ᚓࡽࢀࡓ▱ぢࢆ⤫ྜ῝໬ࡉࡏࡿࡇ࡜࡛ࡑࢀࡒࢀࡢ⣔࡟࠾࠸࡚ࡉࡽ࡞
ࡿ㧗ᛶ⬟໬࡬࡜⧅ࡀࡿࡇ࡜ࡀᮇᚅ࡛ࡁࡿࠋᐇ㦂㸸Mn ࢆ࣮࣋ࢫ࡜ࡍࡿṇᴟᮦᩱࡣࠊඹỿἲ࡟ࡼࡾస〇ࡋࡓ㑄⛣㔠ᒓ」ྜỈ㓟໬≀࡜Ỉ㓟໬ࣜࢳ࣒࢘ࢆ࣮࣑࡛࣎ࣝࣝΰྜࡋࡓᚋࠊ✵Ẽ୰࡛↝ᡂࡋ࡚ᚓࡽࢀࡿ Li2MnO3-LiCo1/3Ni1/3Mn1/3O2 ⣔ࡢヨᩱࢆ⏝࠸ࡓࠋSi ࢆ࣮࣋ࢫ࡜ࡍࡿ㈇ᴟᮦᩱࡣࢼࣀࢧ࢖ࢬ Si㻔100 nm ௨ୗ㻕ࠊ㯮㖄ࠊᑟ㟁ຓ๣࡛࠶ࡿࢣࢵࢳ࢙ࣥࣈࣛࢵࢡࠊ⤖╔๣࡜ࡋ࡚࣏ࣜࣇࢵ໬ࣅࢽࣜࢹࣥ㻔PVdF㻕ࡶࡋࡃࡣ࣏ࣜ࢔ࢡࣜࣝ㓟ࢼࢺ࣒ࣜ࢘㻔PANa㻕ࢆ⏝࠸ࠊࡑࡢ㔜㔞ẚࢆ 20:40:10:30 ࡜ࡋ࡚స〇ࡋࡓࠋNa ࢖࢜ࣥ㟁ụ࡟ࡘ࠸࡚ࡣࠊࢡࣞࣁ㻔ᰴ㻕〇ࣁ࣮ࢻ࣮࢝࣎ࣥ࡜ PVdF ࢆ 9:1 㔜㔞ẚࡢ๭ྜ࡛ΰྜࡋ࡚ࠊ㟁ᴟࢆస〇ࡋࡓࠋࡲࡓ୍㒊ࡢヨᩱ࡛ࡣ㟁Ẽ໬Ꮫࢭࣝࢆస〇ࡋ࡚㟁Ẽ໬Ꮫⓗ࡟㓟໬/㑏ඖࡍࡿࡇ࡜࡟ࡼࡾㄪ〇ࡋ࡚ ᐃヨᩱ࡜ࡋࡓࠋ
HAXPES ࡢ ᐃ᮲௳ࡣḟࡢ࡜࠾ࡾ࡛࠶ࡿࠋບ㉳࢚ࢿࣝࢠ࣮㸸7.9499 keVࠊ࢔ࢼࣛ࢖ࢨ࣮ࡢࣃࢫ࢚
ࢿࣝࢠ࣮㸸100eV. ㏻ᖖࡢ Mg Kα ⥺ࢆ⏝࠸ࡿ㌾ X ⥺ග㟁Ꮚศගἲ㻔SX-PES㻕ࡣᕷ㈍ࡢ⿦⨨㻔JEOL,JPS-9010MC㻕ࢆ⏝࠸࡚⾜ࡗࡓࠋIntensity/ A.U.
㻌

Intensity/ A.U.
㻌

Intensity/ A.U.
㻌

Intensity/ A.U.
㻌

Intensity/ A.U.
㻌⤖ᯝ࠾ࡼࡧ⪃ᐹ㸸
㻔1㻕 Li ࢖࢜ࣥ㟁ụ⏝㟁ᴟࡢ᪂つṇ㈇ᴟ๣ࡢ཯ᛂᶵᵓࡢゎ᫂
Fig.1 ࡟㧗ᐜ㔞ṇᴟᮦᩱ࡜ࡋ࡚ᮇᚅࡉࢀ࡚࠸ࡿ Li2MnO3-LiCo1/3Ni1/3Mn1/3O2 ⣔ṇᴟᮦᩱ࡟㛵ࡋ࡚SX-PES ࡜ HAXPES ࢆ⏝࠸ࡓሙྜࡢ ᐃ⤖ᯝࢆẚ㍑ࡋ࡚♧ࡍࠋᨺ㟁≧ែ࡟╔┠ࡍࡿ࡜ࠊSX-PES
࡛ࡣࠊMn 2p ࢫ࣌ࢡࢺࣝ࡟ぢࡽࢀࡿࡼ࠺࡟ࣆ࣮ࢡᙉᗘࡀ㠀ᖖ࡟ᙅ࠸ࡇ࡜ࡀࢃ࠿ࡿࠋࡇࢀࡣࠊึᅇ඘㟁᫬࡟ᅛయ୰࠿ࡽᨺฟࡉࢀࡓ㓟⣲ࡀᨺ㟁᫬࡟㟁Ẽ໬Ꮫⓗ࡟㑏ඖࡉࢀ㟁ᴟ⾲㠃࡟ሁ✚ࡋ࡚ࡋࡲ࠺
ࡇ࡜࡟⏤᮶ࡋ࡚࠸ࡿ[1]ࠋ⤖ᯝ࡜ࡋ࡚ SX-PES ࢆ⏝࠸࡚ ᐃࢆ⾜ࡗࡓሙྜࠊࣉ࣮ࣟࣈ῝ࡉࡀὸ࠸ࡓࡵ࡟㓟໬≀ࣂࣝࢡࡢほ ࡀ㠀ᖖ࡟ᅔ㞴࡛࠶ࡗࡓࠋࡑࡇ࡛ HAXPES ࢆ⏝࠸࡚ྠࡌヨᩱࢆ ᐃࡋࡓ࡜ࡇࢁࠊሁ✚≀⏤᮶ࡢᙉᗘࡀ኱ࡁࡃῶᑡࡋࠊ㠀◚ቯ࡛㓟໬≀ࣂࣝࢡ࠿ࡽࡢ᝟ሗࢆᚓࡽࢀࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋࡲࡓࠊMn 1s ࡣࡑࡢ⤖ྜ࢚ࢿࣝࢠ࣮ࡀ 6539eV ࡜㧗ࡃࠊHAXPES ࢆ⏝࠸ࡿࡇ࡜࡛ึࡵ࡚
ᐃࢆ⾜࠺ࡇ࡜ࡀ࡛ࡁࡓࠋࡇࡢ Mn 1s ࡢ ᐃ࡟ࡼࡾ X ⥺྾཰ศගἲ㻔XAS㻕࡜ẚ㍑ࡋ࡚ࡼࡾ┤᥋ⓗ࡞ Mn ࡢ㓟໬ᩘࡢኚ໬ࡀほ ࡛ࡁࡿࡼ࠺࡟࡞ࡿࡇ࡜ࡀᮇᚅࡉࢀࡿࠋ


Mg Kᶽ
Mg Kᶽ

Mn 2p3/2
O 1s CO3
4.8 V

4.8 V
recharged
rechaeged



2.0 V

2.0 V

pristine
pristine

540
535
530
525
660
650640BE 㻌/ eVBE 㻌/ eV
HAXPES
HAXPES㻌HAXPES㻌HX-PES
HX-PES
HX-PES
Mn 2p3/2
O 1s
Mn 1s


4.8V

recharged
2.0V
2.0V2.0Vpristine
pristinepristine


660
650
640
540535530
5256550 6545 6540 6535
BE 㻌/ eVBE 㻌/ eVBE 㻌/ eV
Fig.1 A Comparison between SX-PES 㻔upper㻕 and HAXPES 㻔lower㻕
for the Li1.2Ni0.13Co0.13Mn0.54O2 electrodes.





Energy of Photo Electron / eV




Intensity / C.P.S

6087

80000

㻌
6095

6091

6099

Si 1s6103PANa

PVdF
40000

01852



1844
1848
1840

Binding Energy / eV

1836

Fig.2 HAXPES Si 1s spectra of the Si/Graphite composite electrodes with PVdF andPANa polymer binders.

㻌㻌

Capacity / mAh g

Voltage / V-1

୍᪉ࠊFig.2 ࡟ࡣ㧗ᐜ㔞㈇ᴟ๣࡜ࡋ࡚ὀ┠ࡉࢀ࡚࠸ࡿ Si ⣔ྜ㔠㟁ᴟࡢࠊSi 1s ࡢ HAXPES ᐃ⤖ᯝࢆ♧ࡋࡓࠋSi ⣔ྜ㔠⣔ࡢḞⅬࡣࢧ࢖ࢡࣝ≉ᛶࡀඃࢀ࡞࠸࡜࠸࠺ࡇ࡜࡛࠶ࡗࡓࡀࠊᡃࠎࡣࡇࢀࡲ
࡛࡟ Si ⢊ᮎ࠿ࡽྜ๣㟁ᴟࢆసᡂࡍࡿ㝿࡟⏝࠸ࡿ⤖╔๣ࡢᙳ㡪࡟㛵ࡋ᳨࡚ウࢆ⾜࡞ࡗ࡚ࡁࡓࠋ
HAXPES ࢆ⏝࠸࡚ Si 1s ࡢ ᐃࢆ⾜ࡗࡓ⤖ᯝࠊ㟁ᴟ≉ᛶ࡟ඃࢀ࡞࠸ PVdF ࢆ⏝࠸࡚ ᐃࢆ⾜ࡗࡓ⤖ᯝࠊࢳ࣮ࣕࢪ࢔ࢵࣉࡢᙳ㡪ࡀ㠀ᖖ኱ࡁ࠸ࡇ࡜ࡀࢃ࠿ࡗࡓࠋ୍᪉࡛㟁ᴟ≉ᛶ࡟ඃࢀࡿ PANa ࡢሙྜ࡟ࡣࢳ࣮ࣕࢪ࢔ࢵࣉࢆ㉳ࡇࡉ࡞࠸㏻ᖖࡢࢫ࣌ࢡࢺࣝࡀほ ࡉࢀࡓࠋࡇࢀࡣ Si ࡢ㟁ᴟ࡟࠾ࡅࡿ㏻㟁
ᛶࡀⰋ࠸ࡇ࡜ࢆ♧၀ࡋ࡚࠾ࡾࠊヲ⣽࡞᳨ウࢆ⾜ࡗࡓ⤖ᯝࠊ⤖╔๣ࡢ✀㢮࡟ࡼࡾᮦᩱࡢศᩓᛶࡀ኱ࡁࡃᙳ㡪ࡍࡿࡇ࡜ࡀࢃ࠿ࡾࡘࡘ࠶ࡿࠋHAXPES ࢆ⏝࠸ࡿࡇ࡜࡛ Si ࡢศᩓ≧ែࢆ┤᥋ⓗ࡟ほ ࡍࡿࡇ࡜ࡀྍ⬟࡛࠶ࡾࠊ㟁ᴟ≉ᛶホ౯ࢆ⾜࠺࡟࠶ࡓࡾ㠀ᖖ࡟᭷⏝࡞ᡭἲ࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ
㻔2㻕 Na ࢖࢜ࣥ㟁ụ⏝㟁ᴟࡢᅛయ⓶⭷࡜ᮦᩱࣂࣝࢡ࡟㛵ࡍࡿศᯒ
࣏ࢫࢺ Li ࢖࢜ࣥ㟁ụࢆᚿྥࡋ࡚ࠊࣞ࢔࣓ࢱࣝࣇ࣮ࣜࡢᮦᩱࡔࡅ࡛㟁ᴟࢆᵓᡂࡍࡿ᪂ࡋ࠸㟁ụࠊࠕNa ࢖࢜ࣥ㟁ụࠖࢆᐇ⌧ࡍࡿࡓࡵ࡟ࡣࠊྍ㏫ⓗ࡟ Na ࢖࢜ࣥࡢ྾ⶶ/ᨺฟࡀྍ⬟࡛࠶ࡿ㈇ᴟᮦᩱࢆⓎぢࡋ࡞ࡅࢀࡤ࡞ࡽ࡞࠸࡜࠸࠺኱ࡁ࡞ㄢ㢟ࡀᏑᅾࡋ࡚࠸ࡓࠋᡃࠎࡣ㈇ᴟά≀㉁࡜ࡋ࡚ࣁ࣮ࢻ࣮࢝࣎
ࣥ㸦㞴㯮㖄໬ᛶⅣ⣲㸧ࢆ౑⏝ࡋࠊNa ⣔࡟࠾࠸࡚ࡶ 250 mAh g-1 ࡢ㧗ᐜ㔞ࡀྍ㏫ⓗ࡟ᚓࡽࢀࡿࡇ࡜
㻔Fig.3 㻔a㻕㻕ࠊࡉࡽ࡟㐺ษ࡞㟁ゎᾮ࡜ࡢ⤌ࡳྜࢃࡏ࡟ࡼࡾ㛗ᮇ࡟ΏࡾᏳᐃࡋࡓ඘ᨺ㟁ࡀྍ⬟࡜࡞ࡿࡇ࡜ࢆୡ⏺࡛ึࡵ࡚ぢฟࡋ࡚࠸ࡿ㻔Fig.3 㻔b㻕㻕[2]ࠋ

㻌
㻌

㻟㻜㻜

㻞㻚㻜

㻞㻡㻜
㻝㻚㻡

㻞㻜㻜

㻝㻚㻜

㻝㻡㻜

㻜㻚㻡

㻝㻜㻜

㻜㻚㻜

㻡㻜
㻜
㻡㻜
㻝㻜㻜
㻝㻡㻜
㻞㻜㻜
㻞㻡㻜
㻝㻜 㻞㻜 㻟㻜 㻠㻜 㻡㻜 㻢㻜 㻣㻜 㻤㻜 㻥㻜 㻝㻜㻜
-1Cycle NumberCapacity / mAh g㻔b㻕㻔a㻕
in reversible capacities 㻔b㻕 for hard-carbon electrodes inFig.3 Charge-discharge curve 㻔a㻕 and variation
PC solution containing 1 mol dm-3 NaClO4.
Intensityࡑࡢඃࢀࡓ㟁ụ≉ᛶࡣࣁ࣮ࢻ࣮࢝࣎ࣥ㈇ᴟ⾲㠃࡟⏕ᡂࡍࡿᅛయ⓶⭷ࡀ኱ࡁࡃ㛵ಀࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࡇ࡜࠿ࡽࠊࡇࢀࡲ࡛࡟ SX-PES ࢆ⏝࠸ࡓ ᐃ࡜ゎᯒࢆ⾜ࡗ࡚ࡁࡓࠋFig.4a㸧 ࡟ SX-PES 㻔MgKĮ㻕 ࡟ࡼࡾᚓࡽࢀࡓ C 1s ࢫ࣌ࢡࢺࣝࡢ⤖ᯝࢆ♧ࡍࠋࣁ࣮ࢻ࣮࢝࣎ࣥ⏤᮶ࡢ C-C ⤖ྜࢆ♧ࡍࣆ࣮ࢡ㻔284 – 285 eV㻕ࡣ࡯࡜ࢇ࡝☜ㄆ࡛ࡁࡎࠊࣁ࣮ࢻ࣮࢝࣎ࣥ⾲㠃ࡀ⓶⭷࡟ࡼࡗ࡚そࢃࢀ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡇࡢࡇ࡜࠿ࡽ⓶⭷ࡢཌࡉࡣ SX-PES ࡢ᳨ฟ῝ࡉ㻔㹼4 nm㻕ࡼࡾࡶཌ࠸࡜࠸࠺ࡇ࡜ࡀࢃ࠿ࡿࠋ
୍᪉ࠊHAXPES ࡛ྠᵝࡢヨᩱࢆ⏝࠸࡚ ᐃࢆ⾜ࡗࡓ࡜ࡇࢁࠊ⓶⭷ࡢ᝟ሗ࡟ຍ࠼ C-C ⤖ྜ࡟⏤᮶ࡍࡿࣆ࣮ࢡࢆ㢧ⴭ࡟ほ ࡋࠊࡑࡢ⓶⭷ࡢୗ࡟Ꮡᅾࡍࡿࣁ࣮ࢻ࣮࢝࣎ࣥ࠿ࡽࡢ᝟ሗࢆᚓࡿࡇ࡜࡟ᡂ
ຌࡋࡓ㻔Fig.4b㻕㻕ࠋࡇࡢ⤖ᯝࡼࡾᅛయ⓶⭷࡜㟁ゎᾮ࡟㛵ࡋ࡚ SX-PES ࡜ HAXPES ࢆ⤌ࡳྜࢃࡏ࡚ᐃࡍࡿࡇ࡜࡟ࡼࡾࠊࡼࡾヲ⣽࡞▱ぢࡀᚓࡽࢀࡿࡔࡅ࡛ࡣ࡞ࡃࠊࡑࡢ⓶⭷ࡢୗ࡛Ᏻᐃ໬ࡉࢀ࡚࠸ࡿࣁ࣮ࢻ࣮࢝࣎ࣥෆ࡟྾ⶶࡉࢀࡓ Na ࡟㛵ࡍࡿ㟁Ꮚ≧ែࡢ᳨ウࡀྍ⬟࡟࡞ࡿࡇ࡜ࢆ♧၀ࡍࡿ⤖ᯝ࡛࠶ࡿࠋNaO-(CO)O-CH2-R
PVdFPVdF
Na2CO3C-H C-Ca)b)c)㻞㻥㻢 㻞㻥㻠 㻞㻥㻞 㻞㻥㻜 㻞㻤㻤 㻞㻤㻢 㻞㻤㻠 㻞㻤㻞
Binding Energy / eVFig.4 a㻕 SX-PES and b㻕 HAXPES spectra of the hard-carbon electrode after the fifthcycle in a Na cell. SX-PES spectrum of the as-prepared electrode is also shown in c㻕.
௒ᚋࡢㄢ㢟㸸ࡇࢀࡲ࡛ࡢ ᐃ⤖ᯝ࡟ࡼࡾࠊ᳨ฟ῝ࡉࡀ῝࠸ HAXPES ࢆ⏝࠸ࡿࡇ࡜࡛ࠊ㟁ụᮦᩱࡢゎᯒࢆ⾜࠺ୖ࡛㠀ᖖ࡟㔜せ࡜࡞ࡿ⾲㠃⓶⭷ࡸ⏕ᡂయ✚≀ࡔࡅ࡛ࡣ࡞ࡃࠊࡑࡢୗ࡟㞃ࢀ࡚࠸ࡿᅛయෆ㒊࠿ࡽࡢ᝟ሗࢆ㠀◚ቯ࡛ᚓࡽࢀࡿࡇ࡜ࡀࢃ࠿ࡾࡘࡘ࠶ࡿࠋࡇࢀ࡟ࡼࡾࠊࡇࢀࡲ࡛ࡣ୙ྍ⬟࡛࠶ࡗࡓࠊ㓟໬≀ࡢ㟁Ꮚ≧ែࡢゎᯒࢆග㟁Ꮚศග࡟ࡼࡾ⾜࠺ࡇ࡜ࡀྍ⬟࡟࡞ࡿࠋࡲࡓࠊணᮇࡋ࡚࠸࡞࠿ࡗࡓࠊ㟁ᴟࡢศᩓ≧ែࠊ࡟㛵ࡋ࡚ࡶ┤᥋ⓗ࡟ ᐃྍ⬟࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ௒ᚋࠊࡼࡾヲ⣽࡞ࠊࡑࡋ࡚ࠊ⣔⤫ⓗ࡞ ᐃ࡜ゎᯒࡀᚲ㡲࡛ࡣ࠶ࡿࡶࡢࡢࠊHAXPES ࢆ⏝࠸ࡓ ᐃ࡟ࡼࡾࡇࢀࡲ࡛ࡣ୙࡛᫂࠶ࡗࡓ㓟໬≀ࡢ㟁Ꮚ≧ែࠊࣁ࣮ࢻ࣮࢝࣎ࣥ࡟྾ⶶࡉࢀ࡚࠸ࡿ Na ࡢ㟁Ꮚ≧ែ࡞࡝ከࡃࡢ▱ぢࡀᚓࡽࢀࡿࡇ࡜ࡀᮇᚅࡉࢀࠊࡑࡢ⤖ᯝࡣ㟁ụᮦᩱࡢࡉࡽ࡞ࡿ㧗ᛶ⬟໬࡟࠾࠸࡚㠀ᖖ࡟㔜せ࡞ᙺ┠ࢆᯝࡓࡍ࡜ᮇᚅࡋ࡚࠸ࡿࠋཧ⪃ᩥ⊩㸸[1] N. Yabuuchi, S. Komaba et al., J. Am. Chem. Soc., 2011, 133, pp 4404–4419.
[2] ᅜ㝿ฟ㢪␒ྕ㸸 PCT/JP2010/002149