X ⥺྾཰ศᯒࢆ฼⏝ࡋࡓࢼࢺ࣒ࣜ࢘࢖࢜ࣥ஧ḟ㟁ụ⏝ SnS ㈇ᴟࡢ඘ᨺ
㟁཯ᛂᶵᵓࡢゎ᫂႐ከᲄ㩗Ꮚ 1ࠊⓒᓮᜤᏊ 1ࠊYing Ching Lu1ࠊYU Yau Wai Denis2ࠊᑠᯘᰤḟ 1ࠊᒸᓥᩄᾈ 3ࠊ℩ᡞᒣᐶஅ 3ࠊᒸ⏣㔜ே 1
1 ஑ᕞ኱Ꮫࠊ2 㤶ᇛᕷ኱Ꮫࠊ3 బ㈡ LS㸦ᮏᩥ㸧㏆ᖺࠊᏳ౯࡛⎔ቃ㈇Ⲵࡢᑠࡉ࠸ Na ࢆ㈇ᴟ࡟฼⏝ࡋࡓ Na ࢖࢜ࣥ஧ḟ㟁ụࡀὀ┠ࡉࢀ࡚࠸ࡿࠋ
ࡑࡢ㈇ᴟᮦᩱೃ⿵࡜ࡋ࡚ࠊ⌮ㄽᐜ㔞ࡀ኱ࡁࡃẚ㍑ⓗᏳ౯࡛࠶ࡿ Sn ྜ㔠㈇ᴟࡀὀ┠ࡉࢀ࡚࠸ࡿ
[1]ࠋࡋ࠿ࡋ࡞ࡀࡽࠊ୍⯡ⓗ࡞ྜ㔠㈇ᴟࡣ඘ᨺ㟁࡟క࠺኱ࡁ࡞య✚ኚ໬ࡸึᮇ඘ᨺ㟁᫬ࡢ኱ࡁ࡞
୙ྍ㏫ᐜ㔞࡜࠸ࡗࡓㄢ㢟ࢆ᭷ࡋ࡚࠸ࡿࠋࡇࡢㄢ㢟࡟ᑐࡋ࡚ࠊᙜ◊✲ᐊ࡛ࡣࠊSn ஧ඖ໬ྜ≀ࡢ୰࡛ࠊẚ㍑ⓗ㧗࠸㟁Ꮚఏᑟᛶࢆ᭷ࡍࡿ SnS ㈇ᴟ࡬ࡢ㑏ඖࢢࣛࣇ࢙ࣥࡢῧຍ࡟ࡼࡾࠊࢧ࢖ࢡࣝ≉ᛶᨵၿࡀྍ⬟࡛࠶ࡿࡇ࡜ࢆぢฟࡋ࡚ࡁࡓ[2]ࠋࡋ࠿ࡋࠊึᅇ඘ᨺ㟁ࢧ࢖ࢡࣝ୰࡟ 300 mAh/g ࡢ኱ࡁ
࡞୙ྍ㏫ᐜ㔞ࢆ᭷ࡋ࡚࠾ࡾࠊࡇࡢᮦᩱࡢᐇ⏝໬࡟ྥࡅ࡚ࡣ୙ྍ㏫ᐜ㔞ࡢపῶࡀ኱ࡁ࡞ㄢ㢟࡜࡞ࡿࡇ࡜ࡶྠ᫬࡟᫂ࡽ࠿࡜࡞ࡗࡓࠋࡑࡇ࡛ᮏ◊✲࡛ࡣึᅇ඘ᨺ㟁ࢧ࢖ࢡࣝ୰ࡢ඘ᨺ㟁཯ᛂᶵᵓࡢゎ᫂ࢆ㐍ࡵࠊ୙ྍ㏫ᐜ㔞ࡢせᅉࢆ᫂ࡽ࠿࡜ࡋࠊ୙ྍ㏫ᐜ㔞ᨵၿࡢ⣒ཱྀࢆ᥈ࡿࡇ࡜ࢆ┠ⓗ࡜ࡋ࡚࠸ࡿࠋᚓࡽࢀࡓ SnS ㈇ᴟࡢ඘ᨺ㟁ᐃࢆ⾜ࡗࡓ⤖ᯝࠊึᅇᨺ㟁ᐜ㔞ࡣ⣙ 900 mAh/g ࡛࠶ࡿࡢ࡟ᑐࡋࠊึᅇ඘㟁ᐜ㔞ࡣ⣙ 740 mAh/g ࡜࡞ࡾࠊ⣙ 200 mAh/g ࡢ኱ࡁ࡞୙ྍ㏫ᐜ㔞ࢆ᭷ࡋ࡚࠸ࡓࠋࡇࢀࡲ࡛ࡢ᳨ウࡢ⤖ᯝ࠿ࡽࠊึᮇࡢᨺ㟁཯ᛂࡣࠊ͆SnS + 2Na 䋭 Na2S + Sn”ࡢࢥࣥࣂ࣮ࢪࣙࣥ཯ᛂࡀ㐍⾜ࡋࠊࡑࡢᚋ Sn ࡢྜ㔠໬཯ᛂࡀ㐍⾜ࡋ࡚࠸ࡿ࡜᥎ࡉࢀ࡚࠸ࡿࡀࠊᨺ㟁⏕ᡂ≀࡛࠶ࡿ Na2S ࡢ⏕ᡂࡀ㐍⾜ࡋ࡚࠸ࡿࡇ࡜ࢆ♧ࡍሗ࿌౛ࡣ࡞࠸࡞࡝ヲ⣽࡟ࡘ࠸࡚ࡣ࡯࡜ࢇ࡝᫂ࡽ࠿࡜࡞ࡗ࡚࠸
࡞࠸ࠋ௒ᅇࡢሗ࿌࡛ࡣࠊSnS ㈇ᴟࡢ Li ཬࡧࠊNa 㟁ụ≉ᛶ࡟ࡘ࠸࡚ẚ㍑ࡋࠊࡑࡢ඘ᨺ㟁ࡧࠊ඘ᨺ㟁཯ᛂᚋࡢ Sn ཬࡧࠊS ࡢ XANESᐃཬ

ᐃࢆ⾜࠸ࠊࡑࡢ཯ᛂᶵᵓ࡟ࡘ࠸᳨࡚ウࡋࡓ⤖ᯝࢆሗ࿌ࡍࡿࠋ
[1] L. Baggetto, et al., J. Power Source, 234 (2013) 48.
[2] Y. C. Lu, et al., J. Mater. Chem. A, 3 (2015) 16971.
䠴⥺྾཰ศᯒ䜢฼⏝䛧䛯䝘䝖䝸䜴䝮䜲䜸䞁஧ḟ㟁ụ⏝SnS㈇ᴟ䛾඘ᨺ㟁཯ᛂᶵᵓ䛾ゎ᫂႐ከᲄ 㩗Ꮚ 䠄஑ᕞ኱Ꮫ ඛᑟ≀㉁໬Ꮫ◊✲ᡤ䠅ExperimentIntroduction䖃 SnS㈇ᴟ䛾ㄪ〇᪉ἲ䡚Ỉ⇕ྜᡂἲ7)䡚 䖃 䝉䝹ᵓᡂ

⾲1 ᪤ሗ䛾Liཬ䜃Na䜲䜸䞁㟁ụ⏝ྜ㔠⣔㈇ᴟ
SiAl
SnSbPbPGe⾲2 䝇䝈ྜ㔠໬཯ᛂ᫬䛾య✚⭾ᙇ⋡260%1) (Li4.4Sn/Sn)

Li䜲䜸䞁㟁ụ420%2) (Na3.75Sn/Sn)

Na䜲䜸䞁㟁ụ1) B. A. Boukamp, et al., J. Electrochem. Soc., 128 (1981) 725.
2) J. W. Wang, et al., Nano Lett., 12 (2012) 5897.

Li䜔Na䛸䛾ྜ㔠໬཯ᛂ᫬䛻⏕䛨䜛኱䛝䛺య✚ኚ໬䛜䝃䜲䜽䝹ຎ໬䛻ᙳ㡪䜢୚䛘䛶䛔䜛య✚⭾ᙇ䚸จ㞟䜈䛾ᑐᛂ⟇
NaNa

Na
Sn

NaSnS

Na

Sn

Na

Na
Na

NaSn

Na2S

Na3.75Snྜ㔠໬཯ᛂ
671 mAh/g䝁䞁䝞䞊䝆䝵䞁཯ᛂ
356 mAh/g

800

Ỉ⇕ἲ 1 h, 150ΥSnS
Sn:S = 1:1 (molar ratio)+ 20 wt. % AB400 rpm 1 hSnS26)

䖃 XRDཬ䜃XANESᐃ¾ ᐇ㦂ᡭ㡰

4000

pH = 4䡚5SnS/CSnS7)

SnO4)200᧠ᢾ 䜰䞁䝰䝙䜰Ỉ
CH3CSNH2Sn3)600¾ ㈇ᴟ (ሬᕸ㟁ᴟ)ά≀㉁:AB:CMC-Na = 70:20:10 wt. %ά≀㉁: SnS
AB: 䜰䝉䝏䝺䞁䝤䝷䝑䜽 (DENKA)
CMC-Na: Carboxymethyl Cellulose Sodium Salt
¾ ᑐᴟ (I15 mm)
Na㔠ᒓ (Aldrich)¾ 㟁ゎᾮ
1M NaPF6/EC:DEC (1:1 in vol.)1M LiPF6/EC:DMC (1:1 in vol.)¾ 䝉䝟䝺䞊䝍䞊
Glass Fiber Filter (Advantec)¾ 㟁ᅽ⠊ᅖ䞉㟁ὶᐦᗘ
0.01 V-2.0 V, 50 mA/g

SnCl2䞉2H2O
0.25 M 䜽䜶䞁㓟⁐ᾮ㈇ᴟᮦᩱ᥈⣴䛾
᪉ྥᛶ

¾ XRD

ᐃ

1. Ar㞺ᅖẼୗ䛾䜾䝻䞊䝤䝪䝑䜽䝇୰䛷㟁ᴟ䜢ྲྀ䜚ฟ䛩
X-ray powder diffractometer (TTRIII, CuKĮ, Rigaku)
2. ྲྀ䜚ฟ䛧䛯㟁ᴟ䜢24᫬㛫DMC୰䛻ᾐₕ䛧䚸Ὑί䛩䜛 ¾ XANES ᐃ
3. 㟁ᴟ䜢24᫬㛫┿✵஝⇱䛩䜛
బ㈡䝅䞁䜽䝻䝖䝻䞁ග◊✲䝉䞁䝍䞊 (BL 11)

SnO25)

⺯ගἲ S: 2.4 keV

200
400
600
800
Irreversible Capacity (mAh/g)

ᅗ1 ྛ✀䝇䝈໬ྜ≀䛾ᑐNa㈇ᴟ≉ᛶሗ࿌್

Na3.75Sn

NaNa≉ᚩྜ㔠໬䛧䛻䛟䛔
ྜ㔠໬୙⬟
᭱䜒᭷ᮃ
ẘᛶ
ẘᛶ
Ᏻ඲ᛶ
⤒῭ᛶ

Na⣔ྜ㔠㈇ᴟ
㽢㽢
Na3.75Sn: 847 mAh/g
Na3Sb: 660 mAh/g
Na3.75Pb: 485 mAh/g
Na3P: 2560 mAh/g
Na3Ge: 1108 mAh/g
Reversible Capacity (mAh/g)

Li⣔ྜ㔠㈇ᴟ
Li4.4Si: 4200 mAh/g
LiAl: 993 mAh/g
Li4.4Sn: 993 mAh/g
Li3Sb: 660 mAh/g
Li4.4Pb: 569 mAh/g
Li3P: 2560 mAh/g
Li4.4Ge: 1600 mAh/g

Na3.75Sn

Na2S

3) S. Komaba, et al., Electrochem. Commun., 21 (2012) 65.
4) D. Su, et al., Chem. Eur. J., 20 (2014) 3192.
5) D. Su, et al., Phys. Chem. Chem. Phys., 15 (2013) 12543.
6) T. Zhou, et al., ACS Nano, 8 (2014) 8323.
7) Y. C. Lu. et al., J. Mater. Chem. A., 3 (2015) 16971.

◊✲┠ⓗSnS㈇ᴟ䛾ึᅇ୙ྍ㏫ᐜ㔞䛾ᨵၿ䜢┠ᣦ䛧䚸XANES ᐃ䛻䜘䜛SnS㈇ᴟ䛾඘ᨺ㟁཯ᛂᶵᵓ䜢ゎ᫂䛩䜛

ᅗ2 (ᕥ) XANES ᐃ⏝䜾䝻䞊䝤䝪䝑䜽䝇 (ྑ) ヨᩱタ⨨఩⨨Result and Discussion䖃 ᚓ䜙䜜䛯SnS䛾XRD䝥䝻䝣䜯䜲䝹ཬ䜃䚸SEM䜲䝯䞊䝆䖃 ᚓ䜙䜜䛯SnS䛾඘ᨺ㟁᭤⥺ཬ䜃䚸䝃䜲䜽䝹≉ᛶ*ẚ㍑⏝ᕷ㈍SnS (1, 3, 6 h⢊○)21h3 h⢊○1ȝmᅗ4 ㄪ〇䛧䛯SnS䛾FE-SEM⏬ീ
1 h⢊○
ICDD: 065-3812
SnS: Pnma

2030
40
5060
2ș (degree/CuKĮ)7080

ᅗ3 ㄪ〇䛧䛯SnS䛾XRD䝥䝻䝣䜯䜲䝹

Normalized absorption (a. u. )䖃 ඘ᨺ㟁ᚋSnS㈇ᴟ䛾XANES2450

ᐃ

initial0.5 V
0.01 V2.0 V2.5

1.00.5

ᅗ8 XANES ᐃ䛻⏝䛔䛯SnS/Na䛾

2000

ᐃⅬS
Na2SSnS2470
Energy (eV)248020002101 h⢊○
200

400
600
Capacity (mAh/g)

8001020Cycle number30

ᅗ6 ㄪ〇䛧䛯SnS䛾䝃䜲䜽䝹≉ᛶ䞉ᕷ㈍䛾SnS䜢⢊○䛧䛯ヨᩱ䛷䛿䚸⢊○᫬㛫䛜㛗䛟䛺䜛䛻䛴䜜䛶䚸୙ྍ㏫ᐜ㔞䛜ቑຍ䛩䜛䛣䛸䛜᫂䜙䛛䛸䛺䛳䛯

ᅗ5 ㄪ〇䛧䛯SnS䛾ึᅇ඘ᨺ㟁᭤⥺䞉ẚ㍑ⓗ⢏Ꮚᚄ䛜䛭䜝䛳䛶䛔䛯1᫬㛫⢊○ヨᩱ䛸Ỉ⇕ἲ䛷ㄪ〇䛧䛯SnS㈇ᴟ䛾䝃䜲䜽䝹≉ᛶ䛿䚸ẚ㍑ⓗⰋዲ䛷䛒䛳䛯
2.5

1.5

800
1200 1600
Capacity (mAh/g)

4003 h⢊○㟁ᅽ⠊ᅖ: 0.01 V-2.0 V

4006001Na-ion battery

2.002460

6 h⢊○
2䞉ᕷ㈍䛾SnS䜢䝪䞊䝹䝭䝹䛻䛶⢊○䛧䛯ヨᩱ䛷䛿䚸⢊○᫬㛫䜢㛗䛟䛩䜛䛣䛸䛻䜘䜚䚸≀⌮䜶䝛䝹䜼䞊䛻䜘䜛⢏Ꮚᡂ㛗䛜ぢ䜙䜜䜛

Voltage (V vs. Na+/Na)

10䞉Ỉ⇕ἲ䛻䜘䜚䚸༢┦䛾SnS䛜ᚓ䜙䜜䜛䛣䛸䜢☜ㄆ䛧䚸䜎䛯⢏ᚄ䜒1 Pm䛾1ḟ⢏Ꮚ䛜จ㞟䛧䛯ⰼ䜃䜙䛾䜘䛖䛺ᙧ≧䛷䛒䜛䛣䛸䜢☜ㄆ䛧䛯

1

䞉0.5 V䜎䛷䛾ᨺ㟁཯ᛂ䛻䜘䜚䚸Na2S䛻⏤᮶䛩䜛
XANES䝥䝻䝣䜯䜲䝹䛜ᚓ䜙䜜䛯
эSnS + 2Na ֎ Na2S + Sn 䛾䝁䞁䝞䞊䝆䝵䞁2490
཯ᛂ䛜㐍⾜䛧䛶䛔䜛䛸᥎ 䛥䜜䜛

ᅗ7 SnS/Naึᅇ඘ᨺ㟁ᚋ䛾S K-edge XANES 䞉0.5 V௨ୗ䛷䛿䚸XANES䝥䝻䝣䜯䜲䝹䛻ኚ໬䛿
䝇䝨䜽䝖䝹
ぢ䜙䜜䛺䛔

Normalized absorption (a. u. )Intensity (a. u. )6 h⢊○Voltage (V vs. Na+/Na)

26h

Capacity (mAh/g)

Ỉ⇕ἲ

3hỈ⇕ἲ
6 h⢊○
3 h⢊○
1 h⢊○

800

1Ỉ⇕ἲ

2450

initial
0.5 V
0.0 V
2.5 VVoltage (V vs. Li+/Li)Ỉ⇕ἲLi-ion battery

2.0㟁ᅽ⠊ᅖ: 0 V-2.5 V

1.5
1.00.50400

800
1200 1600
Capacity (mAh/g)

ᅗ10 XANES ᐃ䛻⏝䛔䛯SnS/Li䛾
S
Li2S
SnS
2460

2470
Energy (eV)2480

䞉Li䜲䜸䞁㟁ụ䛻䛚䛔䛶䜒䚸Na䜲䜸䞁㟁ụ䛸ྠᵝ䛾඘ᨺ㟁཯ᛂ䛜㐍⾜䛧䛶䛔䜛䜒䛾䛸᥎ 䛥䜜䜛Conclusion䖃Ỉ⇕ἲ䛷ྜᡂ䛧䛯SnS䛿䚸ᆒ୍䛺⢏Ꮚ䛜⏕ᡂ䛧䛶䛚䜚䚸䛭䛾䝃䜲䜽䝹≉ᛶ䜒Ⰻዲ䛷䛒䜛䛣䛸䜢☜ㄆ (ᅗ4, 6)
䖃XANES䛾 ᐃ䜢⾜䛖䛣䛸䛻䜘䛳䛶䚸 0.5 V䜎䛷䛾Naཪ䛿䚸Liᤄධ཯ᛂ䛷䛿䚸ୗグ䛾䜘䛖䛺䝁䞁䝞䞊䝆䝵䞁཯ᛂ䛜㐍⾜䛧䛶䛔䜛䛣䛸䜢☜ㄆ (ᅗ7, 9)
SnS + 2Na+ + 2e- ֎ Na2S + Sn
SnS + 2Li+ + 2e- ֎ Li2S + Sn䞉ᮏ◊✲䛿ᩥ㒊⛉Ꮫ┬䛾ጤク䠄ඖ⣲ᡓ␎ᣐⅬᙧᡂᆺ䝥䝻䝆䜵䜽䝖䠅䛾ᨭ᥼䛻䜘䜚⾜䜟䜜䛯䜒䛾䛷䛩
䞉XANES ᐃ䛿䚸஑ᕞ䝅䞁䜽䝻䝖䝻䞁ග◊✲䝉䞁䝍䞊䛻䛚䛡䜛ㄢ㢟␒ྕ䛂1502001A䛃䛻䜘䜚ᚓ䜙䜜䛯ᡂᯝ䛷䛩

ᐃⅬ䞉Na䜲䜸䞁㟁ụ䛾ሙྜ䛸ྠᵝ䛻Li2S䛻⏤᮶䛩䜛
XANES䝥䝻䝣䜯䜲䝹䛜ᚓ䜙䜜䛯 (0.5 V䜎䛷)эSnS + 2Li ֎ Li2S + Sn 䛾䝁䞁䝞䞊䝆䝵䞁཯ᛂ䛜㐍⾜䛧䛶䛔䜛䛸᥎
䛥䜜䜛
2490

ᅗ9 SnS/Liึᅇ඘ᨺ㟁ᚋ䛾S K-edge XANES䝇䝨䜽䝖䝹Acknowledgement

2000