Stoichiometric LiMnO Supporting Information for 2 and … · Supporting Information for Metastable...
Transcript of Stoichiometric LiMnO Supporting Information for 2 and … · Supporting Information for Metastable...
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Supporting Information for
Metastable and Nanosize Cation-Disordered Rocksalt-type Oxides; Revisit on
Stoichiometric LiMnO2 and NaMnO2
Takahito Sato1, Kei Sato1, Wenwen Zhao1,2, Yoshio Kajiya3 and Naoaki Yabuuchi1,2,4*
1Department of Applied Chemistry, Tokyo Denki University, 5 Asahicho Senju, Adachi, Tokyo
120-8551, Japan
2Elements Strategy Initiative for Catalysts and Batteries, Kyoto University, f1-30 Goryo-Ohara,
Nishikyo-ku, Kyoto 615-8245, Japan
3Technology Department, Electronic Materials Group, JX Nippon Mining & Metals Corporation,
1-2, Otemachi 1-Chome, Chiyoda-ku, Tokyo 100-8164, Japan
4Department of Chemistry and Life Science, Yokohama National University, 79-5 Tokiwadai,
Hodogaya-ku, Yokohama, Kanagawa 240-8501
*Corresponding Author
E-mail: [email protected]
Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A.This journal is © The Royal Society of Chemistry 2018
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20 40 60 80 100
600 rpm, 12 h
600 rpm, 24 h
221
021
200
11001
0
220
200
2deg. (Cu K)
600 rpm, 36 h111
Before mechanical millinga = 4.583 Å, b = 5.760 Å,c = 2.814 Å, V = 74.30 Å3
a = 4.166 Å,V = 72.28 Å3
Figure S1. Changes in XRD patterns from zigzag-layered LiMnO2 to rocksalt LiMnO2 during
mechanical milling.
40 60 80 100
calculated observed difference
2/ deg. (Cu K)
Formula Rocksalt-type Li1.0Mn1.0O2
Space group Fm-3m, a = 4.153(5) Å
Rwp = 8.72%, RB = 6.80%
Atom Site x y z B / Å2 g
Li 4a 0 0 0 0.4 0.42
Mn 4a 0 0 0 0.4 0.5
O 4b 0.5 0.5 0.5 1.5 1.0
Figure S2. A fitting result of rocksalt LiMnO2 by Rietveld analysis. Note that the presence of
defects at Li sites is considered for the analysis, which is further discussed in the later section.
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10th
0 50 100 150 200
1
2
3
4
5
10th
Volta
ge
/ V
Capacity / mA h g-1
10th
1.5 - 4.8 V, 10 mA g-1, at R.T.
Figure S3. Charge/discharge curves of 10th cycle for zigzag layered LiMnO2.
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1.0
2.0
3.0
4.0
5.0285 mA h g-1
As-prepared rocksalt LiMnO2
Theoretical capacity based on Li-contents
10th
Volta
ge /
V
1st
After Mixing with AB10th 1st
0 50 100 150 200 250 300
1.0
2.0
3.0
4.0
5.0
Volta
ge /
V
Capacity / mA h g-1
Figure S4. Charge/discharge curves of rocksalt LiMnO2 before/after mixing with AB by ball milling
at 10 mA g-1.
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After Mixing with AB
2 µm
2 µm
As-prepared rocksalt LiMnO2
Mn
C
Mn/C
Figure S5. Comparison of SEM images of rocksalt LiMnO2 before/after mixing with AB by ball
milling. EDX mappings of the sample after milling with AB are also shown. Carbon is uniformly
distributed in the sample after milling.
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10 20 30
22020
0
Full discharge
Full charge
2deg. ( = 0.5003 Å)
Pristine
Charge to 100 mA h g-1
a = 4.173 Å, V = 72.67 Å3
a = 4.104 Å, V = 69.12 Å3
a = 4.072 Å, V = 67.52 Å3
a = 4.172 Å, V = 72.62 Å3
111
0 50 100 150 200 2501
2
3
4
5
Volta
ge
/ V
Capacity / mA h g-1
1.5 - 4.8 V, 10 mA g-1, R.T.
Figure S6. Ex-situ synchrotron XRD patterns of rocksalt LixMnO2 for the initial charge/discharge
process.
20 40 60 80 100
Al
5th cycle
2deg. (Cu K)
Pristine
1st cycle
Al
* : Sample holder
AlAl
Figure S7. Changes in XRD patterns of rocksalt LixMnO2 upon electrochemical cycles.
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40 60 80 100
220
200
* : Al foil
a = 4.085 Å, V = 68.16 Å3
a = 4.418 Å, V = 86.24 Å3
*
Full discharge
2 / deg. (Cu K)
Full charge
*
Pristine
a = 4.420 Å, V = 86.33 Å311
1
Figure S8. Changes in XRD patterns of rocksalt NaxMnO2 for the initial charge/discharge process.
6540 6560 6580
Nor
mal
ized
Inte
nsity
/ a.
u.
Energy / eV
Mn K-edge Full charge
Full discharge
Mn2O3
MnO2
6540 6542 6544 6546 6548 6550
Energy / eV
Full chargeFull discharge
Figure S9. XAS spectra of fully charged/discharged rocksalt LixMnO2 with Mn2O3 and MnO2 used
as reference materials. Pre-edge data are also highlighted in the inset.
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0 50 100 150 2000.0
1.0
2.0
3.0
4.0
5.0
400 mA g-1
50 mA g-1100 mA g-1
200 mA g-1
20 mA g-1
Volta
ge /
V
Capacity / mA h g-1
Rocksalt NaMnO2
Figure S10. Rate capability of rocksalt NaxMnO2. The cell was charged at 10 mA g-1 and then
discharged at different rates. Sample loading was 1.85 mg cm-2.