SPring-8䉫䊥䊷䊮䉣䊈䊦䉩䊷⎇ⓥળ䋨╙5࿁䋩䌾ੑᰴ㔚ᳰ䈱ᦨ೨✢䌾᡼኿శ䈮䉋䉎㜞ኈ㊂䊥䉼䉡䊛䉟䉥䊮㔚ᳰ᧚ᢱ䈱᭴ㅧ⸃ᨆ䈫ഠൻ⸃ᨆᣣ┙䊙䉪䉶䊦䉣䊅䉳䊷ᩣᑼળ␠ᴡ㊁ ⡡Hitachi Maxell Energy, Ltd. – Confidential and Proprietary

August 29, 2011᡼኿శ䈮䉋䉎䊥䉼䉡䊛䉟䉥䊮㔚ᳰ᧚ᢱ䈱ಽᨆ଀

Hitachi Maxell Energy, Ltd. – Confidential and Proprietary

August29, 20112᡼኿శ䉕↪䈇䈢㔚ᳰ᧚ᢱ䈱ಽᨆ଀䋨ᱜᭂ᧚ᢱ䋩䇼Mn K-edge XANES Profiles of LiMgxMn2-xO4䇽

LiMn2O4䈱Mnṁ಴ૐᷫ䈻䈱⹜䉂

Jahn-Tellerᱡ(Mn3+)䈱ૐᷫ䈏ᔅⷐ
2Mn3+ĺ0Q2++Mn4+䈱෻ᔕᛥ೙0.8

AbsorbanceLiMn2O4䈲㜞᷷⾂⬿䈪䈱Mnṁ಴䈏⺖㗴

1.00.6

LiMg0.02Mn1.98O4
LiMg0.2Mn1.8O4

0.4

LiMn2O4

0.2Mn K-edge

0.0䋨৻଀䋩Mg2+ᷝട䈮䉋䉎Mn3+䈱ૐᷫ6535

6540

6545

6550

6555

6560

6565

Energy / eV

Mg2+ᷝട䈮䉋䉍䇮Mn K-edge䈏㜞䉣䊈䊦䉩䊷䉲䊐䊃Ј Mn3+䈱ૐᷫHitachi Maxell Energy, Ltd. – Confidential and Proprietary

August29, 20113᡼኿శ䉕↪䈇䈢㔚ᳰ᧚ᢱ䈱ಽᨆ଀䋨⽶ᭂ᧚ᢱ䋩㜞ኈ㊂⽶ᭂ᧚ᢱSiOC䈱᭴ㅧ⸃ᨆ䇼Si K-edge XANES Profiles of Si Materials䇽

Si

XANES᷹ቯ䈫TEMⷰኤ䈮䉋䉍䇮⹦⚦䈭᭴ㅧ⸃ᨆ䈏น⢻

Absorbance

SiO䈲XRD⊛䈮䉝䊝䊦䊐䉜䉴䈪䈅䉎䈢䉄䇮⹦⚦䈭᭴ㅧ⸃ᨆ䈏࿎㔍

SiO
SiO2

䇼High Resolution TEM Image of SiO䇽Si Particle (3nm)1830 1840 1850 1860 1870

Photon Energy / eV
SiO2 matrices(amorphous)
Si (111)2nm

SiO䈲Si䈫SiO2䈱ⶄว૕䈪䈅䉍䇮䉝䊝䊦䊐䉜䉴SiO2ਛ䈮䊅䊉Si䈏ಽᢔ䈚䈢᭴ㅧ䈪䈅䉎䈖䈫䈏ಽ䈎䈦䈢䇯
Hitachi Maxell Energy, Ltd. – Confidential and Proprietary

Si ultra fine particles(<20nm)August29, 20114䊥䉼䉡䊛䉟䉥䊮㔚ᳰ᧚ᢱ䈱㜞ኈ㊂ൻ䈮ะ䈔䈢᧚ᢱ㐿⊒

Hitachi Maxell Energy, Ltd. – Confidential and Proprietary

August29, 20115ⷺᒻ䊥䉼䉡䊛䉟䉥䊮㔚ᳰ䈱䉣䊈䊦䉩䊷ኒᐲ㜞లႯൻ┹੎䈱⚳Ὣ →㩷㜞ኈ㊂ᵴ‛⾰䈱㐿⊒ ᔅ㗇

Energy Density / WhL-1600

ᣂⷙᵴ‛⾰䈱ណ↪

550
500
450400ᵴ‛⾰䈱㜞లႯ䊶 㔚ᭂኒᐲ䈱Ⴧട䊶 ኈ㊂䈮ነਈ䈚䈭䈇ㇱ᧚૶↪㊂䈱ૐᷫCalculate from prismatic cell350

'03 '04 '05 '06 '07 '08 '09 '10 '11 '12
Calendar Year

Hitachi Maxell Energy, Ltd. – Confidential and Proprietary

August 29, 2011

Discharge Potential / V vs Li/Li+ฦ⒳䊥䉼䉡䊛䉟䉥䊮㔚ᳰ᧚ᢱ
4.1
4.0

䇼Cathode Materials䇽
LiMn2O4
LiCoO2

3.9
3.8

LiNi1/3Co1/3Mn1/3O2
LiNiO2

LiNi0.8Co0.15Al0.05O2

Graphite

0.4

LiVO2

0.6

CoSn

LiSiO
Si
Sn
Li2.6Co0.4N

1.0
1.2

3.5
3.4

0.2

0.8

3.7
3.6

0.0

䇼Anode Materials䇽

LiFePO4

1.4

1.6
3.3
300 400 500 600 700 800 900 0

L4Ti5O12500 1000 1500 2000 2500
-1

Specific Discharge Capacity / mAhcc

Hitachi Maxell Energy, Ltd. – Confidential and Proprietary

August 29, 2011㜞ኈ㊂䊥䉼䉡䊛䊶䊆䉾䉬䊦㉄ൻ‛䈱᭴ㅧഠൻ⸃ᨆ䈫᭴ㅧ቟ቯൻ

Hitachi Maxell Energy, Ltd. – Confidential and Proprietary

August29, 20118㜞ኈ㊂ൻ䈮ะ䈔䈢ᱜᭂ᧚ᢱ䈱ត⚝NiᲧ₸Ⴧᄢ䈫䈫䉅䈮4.2 V䈪䈱Liᒁ䈐ᛮ䈐㊂Ⴧട Ј 4.2 V♽䈪䈱㜞ኈ㊂ൻ
㩷

Potential / V vs. Li/Li+

5.2
Voltage profiles calculated using
electrochemical density of statezφ(1 - 2 xi ) - 2 RT ln xi
E ( x ) = E0i FF
1 - xi

4.8
4.4

T.Ohzuku and A.Ueda, J.Electrochem.Soc.,144, 2780(1997)

4.2

4.0

LiCoO2

LiNiO2

3.6
High capacity

3.2200 mAh g-1

LiCo1/4Ni3/4O2
150 mAh g-1

LiCo3/4Ni1/4O2

2.8
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0x in LixMeO2Hitachi Maxell Energy, Ltd. – Confidential and Proprietary

August 29, 2011

NiᲧ₸90%ㄭற䈪4.2 V♽䈪ᦨ㜞ኈ㊂220
200

LiCoxNi1-xO2 with x = ca.0.1 show
the highest capacity

180160㩷-1
Rechargeable capacity / mAh gNi/CoᲧ₸䈫᡼㔚ኈ㊂䈱㑐ଥ㩷

140
120
10001.00.9

0.80.70.60.50.40.30.20.10.0x in LiCoxNi1-xO2
Hitachi Maxell Energy, Ltd. – Confidential and Proprietary

August 29, 2011

LiNiO2䈱㔚૏ᒻ⁁䊶ਇนㅒኈ㊂䈱ᷫዋ Ј NiᲧ₸90%䈪ᦨ㜞ኈ㊂
㩷

LiNi0.8Co0.2O2

3

㩷

LiNi0.9Co0.1O2

4

More than 200 mAh g-1 ofrechargeable capacity

3

LiNiO2

4

㩷Potential / V vs. Li/Li+㩷43

Examined in lithium cell

050

100

150-1

Capacity / mAh gHitachi Maxell Energy, Ltd. – Confidential and Proprietary

200250August 29, 2011

LiNi0.9Co0.1O2䉕↪䈇䈢ⷺᒻ䊥䉼䉡䊛䉟䉥䊮㔚ᳰ䈱⺖㗴
LiNi0.9Co0.1O2䉕↪䈇䈢ⷺᒻ䊥䉼䉡䊛䉟䉥䊮㔚ᳰ䈱䉰䉟䉪䊦․ᕈ

110

Capacity retention / %LiNi0.9Co0.1O2 / Graphite
Prismatic Cell (463443)

100䉰䉟䉪䊦ഠൻ䈏⺖㗴

9080
7060
50

Nominal capacity : ca. 850 mAhCurrent : 0.7 C rate (charging), 1 C rate(discharging)
Voltage ranges : 2.5 to 4.2 V
(n=3)

0100

200
300
Cycle number / -Hitachi Maxell Energy, Ltd. – Confidential and Proprietary

400

500

August 29, 2011

LiNi0.9Co0.1O2䉕↪䈇䈢ⷺᒻ䊥䉼䉡䊛䉟䉥䊮㔚ᳰ䈱⺖㗴㔚ᳰ䉕⸃૕䈚䇮ᱜᭂ䉕ᛂ䈤ᛮ䈒ᛂ䈤ᛮ䈇䈢ᱜᭂ䉕DMEṁᇦ䈪ᵞᵺ䇮ੇ῎

4.0䍙䍐䍖䍷೨3.5㩷䍙䍐䍖䍷೨
500䍙䍐䍖䍷ᓟ2.5 V䈮᡼㔚

Potential / V vs. Li/Li+ⷺᒻLIBⷺᒻLIB4.5㩷ኻᭂLi䉶䊦䈪䈱ኈ㊂᷹ቯ⚿ᨐ

3.0500 䍙䍐䍖䍷ᓟ

2.52.00

ኻᭂLi䉶䊦ኈ㊂᷹ቯ
Hitachi Maxell Energy, Ltd. – Confidential and Proprietary

4080

120

160

200-1240

Capacity / mAh gᱜᭂᵴ‛⾰䈱ഠൻ䈏䉰䉟䉪䊦ഠൻⷐ࿃䈪䈅䉎䈫⠨䈋䉌䉏䉎August 29, 2011

LiNi0.9Co0.1O2䈱᭴ㅧ⸃ᨆ(TG, XRD)
TG䋺800͠એ਄䈪㉄⚛᡼಴XRD䋺800͠એ਄(900͠)䈪὾ᚑ䈜䉎䈫ⓍಽᒝᐲᲧI(003)/I(104)䈏ૐਅЈLiጀ䈮Ni䈏ᷙ౉䇼XRD patterns of LiNi0.9Co0.1O2䇽

䇼TG curves of LiNi
㩷
0.9Co0.1O2䇽
0a=2.8709 Å
c=14.1530 Å
c/a=4.930

1

I(003)/I(104)=1.22(108)
(110)
(113)

(107)

(105)

㪿㪼㪸㫋㪼㪻㩷㪸㫋㩷㪐㪇㪇㫆㪚㩷㪽㫆㫉㩷㪍㪿㩷㫀㫅㩷㪸㫀㫉

800͠એ਄䈪᭴ㅧᄌൻ4(101)
(006)
(102)

LiNi0.9Co0.1O2

3a=2.8798 Å
c=14.1435 Å
c/a=4.911

(104)

(003)

2㩷

Weight loss / %LiNi0.9Co0.1O2

I(003)/I(104)=0.97
Liጀ䈻䈱Niᷙ౉䉕␜ໂ

50200

400

600

800 1000oTemperature / C

10Hitachi Maxell Energy, Ltd. – Confidential and Proprietary

20

30

4050

2θ / degree

6070(CuKα)

August 29, 2011

LiNi0.9Co0.1O2䈱᭴ㅧ⸃ᨆ(XAFS)䇼FT of Ni K-edge spectra of Li䌎䌩0.9Co0.1O2䇽
㩷1.00.8

Ni K-edge

ㅘㆊᴺ20

FT intensity / -Normalizedrmaliabsorbance / -@Spring-8(BL16B2)

NiO

0.60.416╙ੑㄭធ

Ni - Ni128355

LiNi0.9Co0.1O2
LiNi0.9Co0.1O2 heated at 900oC for 6h in air
8360

8365

Energy / eV

8370

8375

╙৻ㄭធ80.20.0

LiNi0.9Co0.1O2
LiNi0.9Co0.1O2 heated at 900oC for 6h in air

㩷䇼Ni K-edge XANES Profiles of Li䌎䌩0.9Co0.1O2䇽

Ni - O

4001234

R / Å5Ni-O[㸈]Liጀ䈻ᷙ౉䈚䈢Ni䈲Ni2+䈪䈅䉎䈫⠨䈋䉌䉏䉎:O: NiNi-O[㸇]Ni-O[Σ]Ni-O[Τ]ӠNi-O[Τ]-Ni-O[Σ]Ni-Ni

LiNi0.9Co0.1O2

1.922 Å2.070 Å0.148 Å2.861 ÅLiNi0.9Co0.1O2 (heated at 900oC)

1.915 Å2.049 Å0.134 Å

2.873 ÅHitachi Maxell Energy, Ltd. – Confidential and Proprietary

August 29, 2011

LiNi0.9Co0.1O2䈱᭴ㅧᄌൻ䊝䊂䊦䃩XRD Ј Liጀ䈻Ni䈏ᷙ౉䃩XAFS Ј Ni2+䈏ሽ࿷㩷

Ni2+

4.0
3.0 LiNi0.9Co0.1O2
㩿㪐㪇㪇㷄䇮ᄢ᳇὾ᚑ㪀

㩷

2.5
4.0
3.5
3.0

Ni2+

㩷3.5

2.50

㩷

Potential / V vs. Li/Li+

4.5

LiNi0.9Co0.1O250

100150-1200250

Capacity / mAh gᏀ䈱䉋䈉䈭᭴ㅧᄌൻ䈲ಽᭂ䈱Ⴧᄢ䇮䈍䉋䈶ల᡼㔚ኈ㊂䈱ᷫዋ䉕᜗䈒

Hitachi Maxell Energy, Ltd. – Confidential and Proprietary

August 29, 2011

LiNi0.9Co0.1O2䈱᭴ㅧ቟ቯൻ
Ni ฽᦭₸ : 90%
Co3+ЈMn4++Mg2+
䈰䉌䈇䋺
㽲Ni䈱Li䍙䍐䍢䈻䈱⒖േ䉕ᛥ೙
㽳Mn4+䈫Mg2+䈱㔚⩄䍨䍼䍵䍻䍛

㬍

Mg2+

Normalized absorbance / -䇼XANES Profiles of LiNi0.9Co0.05Mn0.025Mg0.025O2䇽

Mn4+
Ni2+

LiNi0.9Co0.05Mn0.025Mg0.025O2

1.0

LiNi0.9Co0.05Mn0.025Mg0.025O2
Li2MnO3

0.80.6

(4+)

Mn2O3
(3+)

0.4

Mn K edge

0.20.06530

6540

6550

Energy / eV6560

6570

LiNi0.9Co0.05Mn0.025Mg0.025O2ਛ䈱Mn䈲4ଔ䈪ሽ࿷

Hitachi Maxell Energy, Ltd. – Confidential and Proprietary

August 29, 2011

LiNi0.9Co0.1O2䈱᭴ㅧ቟ቯൻ

After charging at 4.2V in the cell with graphite

LiNi0.9Co0.05Mn0.025Mg0.025O2
LiNi0.9Co0.05Mn0.05O2

LiNi0.9Co0.1O2

Heating rate; 2ºC/min䇼Cycle ability䇽

11110

Capacity retention / %䇼DSC Profiles䇽

Prismatic Cell (463443)

LiNi0.9Co0.05Mn0.025Mg0.025O2

10100

LiNi0.9Co0.05Mn0.05O2990880
LiNi0.9Co0.1O2770

Nominal capacity : ca. 850 mAhCurrent : 0.7 C rate (charging), 1 C rate(discharging)
Voltage ranges : 2.5 to 4.2 V(n=3)

660
550

⊒ᾲ㐿ᆎ᷷ᐲ䈏㜞᷷䍚䍪䍢䋺᭴ㅧ቟ቯൻ

Hitachi Maxell Energy, Ltd. – Confidential and Proprietary

0100

200

300

Cycle number / -400

500Mn, Mgᷝട䈮䉋䉍䍙䍐䍖䍷․ᕈะ਄
60%Ј76%@500cycle

August 29, 2011

LiNi0.9Co0.1O2䈱䉰䉟䉪䊦ഠൻ䊝䊂䊦⴫㕙ᖱႎ䋺XAFS(TEY)(003)

500䍙䍐䍖䍷ᓟ

30

4050

60

2θ / degree

(108)
(110)
(113)

(107)

20(105)10(006)
(102)

(101)

(104)

䍙䍐䍖䍷೨

Normalized absorbance / -䍨䍼䍷䍖ᖱႎ䋺XRD@spring-8

1.00.8500䍙䍐䍖䍷ᓟ0.6

⴫㕙䋨䌾40 nm䋩
䈱Ni㉄ൻᢙૐਅ

0.4䍙䍐䍖䍷೨0.2

Ni K edge
0.070(CuKα)

ICP ⚵ᚑಽᨆ
䊶䍙䍐䍖䍷೨ : Li1.0Ni0.9Co0.1O2
䊶500䍙䍐䍖䍷ᓟ : Li0.6Ni0.9Co0.1O2-x
Ni䈲㜞㉄ൻ⁁ᘒ?
Hitachi Maxell Energy, Ltd. – Confidential and Proprietary

8350

8360

8370

Energy / eV8380

ᱜᭂᵴ‛⾰䈱ᗐቯഠൻ䍱䍡䍼䍷☸ሶ⴫㕙䈮NiO-like ᭴ㅧ↢ᚑ䋨ጤႮ䍢䍼䍰䍐䍻᭴ㅧ䋩Ј㔚᳇ൻቇ⊛䈮ਇᵴᕈЈᛶ᛫⋧August 29, 2011

LiNi0.9Co0.1O2䈱䉰䉟䉪䊦․ᕈᡷ⦟
☸ሶ䈱㜞⚿᥏ൻ䈮䉋䉍Ყ⴫㕙Ⓧૐᷫ䇮䈍䉋䈶⴫㕙ᡷ⾰Ј䉰䉟䉪䊦․ᕈ䈱ᡷ⦟
110

Capacity retention / %Prismatic Cell (463443)

100⴫㕙ᡷ⾰9080
LiNi0.9Co0.05Mn0.025Mg0.025O2
䋨ᡷ⦟೨䋩

70

LiNi0.9Co0.1O260
50

Nominal capacity : ca. 850 mAhCurrent : 0.7 C rate (charging), 1 C rate(discharging)
Voltage ranges : 2.5 to 4.2 V
(n=3)

0100

200
300
Cycle number / -Hitachi Maxell Energy, Ltd. – Confidential and Proprietary

400

500

August 29, 2011

SiOCߩల᡼㔚෻ᔕᯏ᭴Hitachi Maxell Energy, Ltd. – Confidential and Proprietary

August29, 201121

Si-C䉮䊮䊘䉳䉾䊃⽶ᭂ᧚ᢱ
Reducing a volumetric expansion of Li-Si anodematerial for Li insertion
Improving cycleability of Si anodeẔSEM Image of Porous Si-C Compositeẕ

Concept for Porous Composite Particle
Discharge

ChargePoreCyclingȝP

SiCoatingsCarbon material

䋱䋮To use fine Si powder䋲䋮To granulate fine Si and carbon with pore
䋳䋮To coat composites with carbon
Hitachi Maxell Energy, Ltd. – Confidential and Proprietary

August 29, 2011

Si-C䉮䊮䊘䉳䉾䊃䈱㔚ᳰ․ᕈ
50䉰䉟䉪䊦ᓟ䈎䉌ᕆỗ䈭ኈ㊂ഠൻ ĺSi☸ሶ䈱䈘䉌䈭䉎ዊ☸ᓘൻᔅⷐ

㩷

60
50

1.2

20
After 1st discharge㩷 / Ahg-1
Capacity

Si/CF

After 1st charge
by 1Ah/cc

Si/CF/PB

4030

ẔCycle Properties of Porous Si-C Compositeẕ

1.4
Si/Graphite

Expansion Rate of Diameter / %ẔExpansion Rate of Porous Si-C Composite for Cycleẕ

106L ȝP &)3%
(Porosity: 52vol%)1.00.86L ȝP Gr(Porosity: 30vol%)0.60.4Graphite

0.2
Mixture Si and C010203040

Porosity / %50600.0

Hitachi Maxell Energy, Ltd. – Confidential and Proprietary

01020304050

Cycle Number
August 29, 2011

Si⭯⤑䈱䉰䉟䉪䊦․ᕈ
䊚䉪䊨䊮㪪㫀㩷→㩷ᓸ☳ൻ →㩷㪪㫀䉰䉟䉵䈲䈬䈖䉁䈪ዊ䈘䈒䋿→㩷㪊㪇㪇㫅㫄એਅ䈪䈲ᄢ䈐䈭ഠൻ䈭䈚㩷
1.2

Capacity / mAh

1.0

1000nm

0.8
0.6
300nm

0.4

25nm

0.20.005100nm

10 15 20 25 30 35 40 45 50

Cycle Number
Hitachi Maxell Energy, Ltd. – Confidential and Proprietary

August 29, 2011䊅䊉Si䈱ᵴ↪䈫2㊀䈱ⶄวൻ䊚䉪䊨䊮䉰䉟䉵㪪㫀㩷→㩷ᓸ☳ൻ →㩷䊅䊉䉰䉟䉵㪪㫀㩷→㩷ಽᢔⶄวൻ࿎㔍 →㩷㪪㫀㪦
Discharge

PoreCharge
Cycling

Active particle(nano-Si/amorphous)

CoatingsCarbonC
bo materialeAmorphous matrices (X)Nano Si crystalline< 20nmNano Li-Si crystalline䂾 Nano-Si can show improved cycleability
without crumbling.
䂾 Amorphous matrices can reduce theexpansion rate for cycle.
Hitachi Maxell Energy, Ltd. – Confidential and Proprietary

SiO
August 29, 2011

Si᧚ᢱ䈱X✢ๆ෼䉴䊕䉪䊃䊦䋨XANES䋩SiO = Si + SiO2 䋨䈇䈝䉏䉅X✢⊛䈮㕖᥏⾰䋩

Absorbance

Si1820SiO
SiO21830

1840

1850

1860

Photon Energy / eV

Hitachi Maxell Energy, Ltd. – Confidential and Proprietary

1870

1880
August 29, 2011

SiO䈱ᓸ⚦᭴ㅧ䋨䊅䊉Si䋯SiO2䉮䊮䊘䉳䉾䊃䋩‫ޣ‬Schematic Image of SiO‫ޤ‬

SiO2 matrices

SiO2 matrices(amorphous)

Si: 3nm
Si ultra fine particles(<20nm)

Si crystalline
Si (111)20nm

2nm

Reference: Y.Nagao, H. Sakaguchi, T. Esaka, et. al., J. Electrochem. Soc., 151, P.1572 (2004).
A.Hohl et al., J. Non-Cryst. Solids, 320, P.255 (2003).
Hitachi Maxell Energy, Ltd. – Confidential and Proprietary

August 29, 2011

SiO-C䉮䊮䊘䉳䉾䊃䈱ೋ࿁ల᡼㔚ᦛ✢SiO䈫C䈱ⶄวൻ ĺ ೋ࿁ല₸20%UP

2.0

Potential / V vs Li/Li+

SiO-C Composite

1.5

1st Efficiency
= 73%
ȝP

1.0
Mixture SiO and Gr
1st Efficiency

0.5
0.00.0

= 54%

0.2

0.4

0.6

0.8

1.0

Capacity / Ahg-1

Hitachi Maxell Energy, Ltd. – Confidential and Proprietary

1.2

1.4
August 29, 2011

SiO-C䉮䊮䊘䉳䉾䊃䈱䉰䉟䉪䊦․ᕈ

Capacity Retention / %SiO䈫C䈱ⶄวൻ ĺ 䉰䉟䉪䊦․ᕈᄢ᏷%UP
㩷100

SiO-C Composite

80
Si-C Composite

60

Mixture SiOand Graphite

40200

Positive electrode: LiCoO2+LiNi1/3Co1/3Mn1/3O2Current: 0.5C
Temp.: 23͠

204060

Cycle Number

Hitachi Maxell Energy, Ltd. – Confidential and Proprietary

80100
August 29, 2011

SiO䈱ల᡼㔚෻ᔕ䋨Li2O↢ᚑ䋩䃩 Why does the first efficiency of SiO-C
composite increase ?
Experimental
Results

ChargeCapacity/ mAhgg-1

Discharge
Capacity/ mAhgg-1

SiO-C Composite(per weight of SiO)

1200()(2560)
1382(2570)

872((1869))740(1388)

Mixture SiO + Gr
(per weight of SiO)

1st Efficiency/%(10mV䌾1.5V)

7354(Assumption)
SiO + 6.4Li ĺ6L/L4.4 + Li2O (irreversible phase)(Theoretical Value)
Charge Capacity = 3880mAh/g
1st Efficiency = 68%
Hitachi Maxell Energy, Ltd. – Confidential and Proprietary

Inconsistency

August 29, 2011㔚ᳰ᧚ᢱ䈱ಽᨆᣇᴺ
SiO2
matrices

Charge & Discharge
XANES and STEM-EELS→ Li cell
NMR→ Full cell

SiCharge
ChStructural Analysis
Extract the sample in Ar→ Wash with DEC→ Dry and transfer to …

XANES system in Ar
X

Charge to 10mV (Li/Li+)
0.25mA/cm2 CCCV
(until 0.025mA/cm2)

Li-Si-O
matrices(NMR: 4.2V CCCV)LixSi

NMR system in Ar
N

Li-Si-Omatrices

FIB system in Ar
F
STEM system in vac.
SDischarge
Di hDischarge to 3V (Li/Li+)
0.25mA/cm2 CCuusing Ar flow bag
M
Measuring in vac.

uusing atmosphere blocking cell
Measuring in Ar
Muusingatmosphere blocking cell
Measuring in vac.
M

(NMR: 2.5V CC)
SiHitachi Maxell Energy, Ltd. – Confidential and Proprietary

August 29, 2011ల᡼㔚䈚䈢SiO䈱NMR䊒䊨䊐䉜䉟䊦ల㔚⁁ᘒ䊶᡼㔚⁁ᘒ䈇䈝䉏䉅Li4SiO4䈱ሽ࿷䉕⏕⹺㩷㩷

䇼7Li NMR spectra of SiOC䇽䇼29Si NMR spectra of SiOC䇽

Li-Si-O

Si / Li2SiO3
Li4SiO4

SiO2/ LixSi

IntensityIntensity

Discharge

LixSi

ChargeInitial500-50 -100 -150

Chemical Shift / ppm

Hitachi Maxell Energy, Ltd. – Confidential and Proprietary

80 60 40 20 0 -20 -40 -60 -80

Chemical Shift / ppm

August 29, 2011ల᡼㔚䈚䈢SiO䈱STEM-EELSಽᨆ䇼EELS spectra㩷 of SiOC䇽

䇼STEM image of SiOC (discharge state)䇽

( II )(I)

Intensity

(I)

50nm

Si0

Si4+( II )90 100 110 120 130 140 150

Energy / eV

Hitachi Maxell Energy, Ltd. – Confidential and Proprietary

August 29, 2011

SiO䈱Li෻ᔕ䊝䊂䊦
Lithium ion conductor

䃂 Li䃂 Si䃂O

䋨Li2SiO3䋩
Li4SiO4
䋨Li2SiO3䋩

Li4SiO4
Li4SiO4

Li4Si

Li4SiO4SiO2Si

InitialSi
Li4.4Si

ChargeHitachi Maxell Energy, Ltd. – Confidential and Proprietary

Discharge
August 29, 2011

SiO䈱ల᡼㔚෻ᔕ 䋨Li4SiO4↢ᚑ䋩ⶄวൻ䈮䉋䉎ᒝ࿕䈭ዉ㔚䊈䉾䊃䊪䊷䉪 ĺᧄ᧪䈱ల᡼㔚෻ᔕ䈏⚿ᨐ䈮෻ᤋ

Charge Capacity (Qc) and First Efficiency (E1st) of SiO
Experimental Results
Mixture SiO and C: Qc= 2560mAh/g(SiO)ύ E1st= 54%
SiO-C Composite: Qc= 2570mAh/g(SiO)ύ E1st= 73%

Calculated Value (from Analysis)

GoodAgreement

Reaction ᾉ 4SiO + 17.2Li ĺ 6L/L4.4) + Li4SiO4
Qc= 2610mAh/gύ E1st= 76.7%
2Si + 8.8Li ĺ 6L/L4.4)
2SiO2 + 8.4Li ĺ6L/L4.4 + Li4SiO4 (irreversible phase)
Causing a superior battery properties
Causing an increase in Si size
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August 29, 2011䉁䈫䉄㜞ኈ㊂㔚ᳰ᧚ᢱLiNi0.9Co0.1O2䈍䉋䈶SiOC䈮䈧䈇䈩᡼኿శ䉕↪䈇䈢᭴ㅧ⸃ᨆ䉕ⴕ䈦䈢䇯
LiNi0.9Co0.1O2䈲Ni2+䈏Liጀ䈮ᷙ౉䈜䉎᭴ㅧᄌൻ䉕ᒁ䈐⿠䈖䈜䇯
LiNi0.9Co0.1O2䈱䉰䉟䉪䊦ഠൻ䈲☸ሶ⴫㕙ㄭற䈪਄⸥䈱᭴ㅧᄌൻ䈏⿠䈐䈢䈢䉄䈪䈅䉎䇯Mn䈍䉋䈶Mg䈱ᷝട䈮䉋䉎᭴ㅧ቟ቯൻ䇮䈍䉋䈶⴫㕙ᡷ⾰䈮䉋䉍LiNi0.9Co0.1O2䈱䉰䉟䉪䊦․ᕈะ਄䉕ታ⃻䈚䈢䇯SiO䈲Si䈫SiO2䈱ⶄว૕䈪䈅䉍䇮䉝䊝䊦䊐䉜䉴SiO2ਛ䈮䊅䊉Si䈏ಽᢔ䈚䈢᭴ㅧ䈪䈅䈦䈢䇯SiO䈲ల᡼㔚ᓟ䈮Li-Silicate䈏↢ᚑ䈚䈩䈇䈢䇯
Hitachi Maxell Energy, Ltd. – Confidential and Proprietary

August 29, 2011