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1
Supporting Information
Insights into the Structural Effects of Layered Cathode
Materials for High Voltage Sodium-ion BatteriesGui-Liang Xu,1 Rachid Amine,2, 3 Yue-Feng Xu,4 Jianzhao Liu,1,5 Jihyeon Gim, 1
Tianyuan Ma,1, 6 Yang Ren,7 Cheng-Jun Sun,7 Yuzi Liu,8 Xiaoyi Zhang,7 Steve M.
Heald,7 Abderrahim Solhy, 9 Ismael Saadoune,10 Wenjuan Liu Mattis,11 Shi-Gang
Sun,4 Zonghai Chen1,* and Khalil Amine1,*
1Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, IL 60439, USA2 Chemical Engineering Department, University of Illinois at Chicago, Chicago, Illinois 60607, USA3 Materials Science Division, Argonne National Laboratory, 9700 S Cass Ave, Lemont, IL 60439, USA4Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory Physical Chemistry of Solid Surfaces, Department of Chemistry, Xiamen University, Xiamen, 361005, China5Department of Chemistry, Virginia Tech, 900 W Campus Drive, Blacksburg, VA 24061, USA6 Materials Science Program, University of Rochester, Rochester, NY 14627, USA7X-ray Science Division, Argonne National Laboratory, Lemont, IL 60439, USA 8Center for Nanoscale Materials, Nanoscience Technology, Argonne National Laboratory, Lemont, IL 60439, USA9Center for Advanced Materials, Mohammed VI Polytechnic University, Ben Guerir, Morocco10 Materials Science and Nano-engineering Department, Mohammed VI Polytechnic University, Ben Guerir, Morocco11 Microvast Inc., 12603 Southwest Freeway, Stafford, Texas 77477, USA
To whom correspondence should be addressed:
Email: [email protected] (Z.C.) and [email protected] (K.A.)
Electronic Supplementary Material (ESI) for Energy & Environmental Science.This journal is © The Royal Society of Chemistry 2017
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Table S1 Summary on the electrochemical performance of layered NaTMO2
(Tm=Ni, Co, Fe, Mn…) cathode materials for sodium-ion batteries
Materials Rate,
mA/g
1st
coulombic
efficiency
1st charge
Capacity,
mAh/g
Last
Capacity,
mAh/g
Voltage
Range, V
Ref.
P2/O1/O3-NaxNi1/3Co1/3Mn1/3O2 15 95% 150.3 133/50th 2.0-4.4 This work
P2/O1/O3-NaxNi1/3Co1/3Mn1/3O2 100 87.5% 143.6 100/100th 2.0-4.4 This work
O3-NaNi1/3Co1/3Mn1/3O2 12 72% 156 112.3/1st 2.0-4.2 Chem. Mater.
2012, 24, 1846-
1853.
O3-NaNi0.5Mn0.5O2 8 74% 250 25/26th 2.0-4.5 Inorg. Chem.,
2012, 51, 6211-
6220
Fe-doped
O3 NaFe0.2Ni0.4Mn0.4O2
12 95% 136 125/30th 2.0-4.0 ACS Appl. Mater.
Interf. 2015, 7,
8585-8591
O3 NaTi0.5Ni0.5O2 20 87% 117 93/100th 2.0-4.0 Chem. Commun.,
2014, 50, 457-
459
Li-doped O3
NaLi0.07Ni0.26Mn0.4Co0.26O2
25 81.2% 181 128/50th 1.5-4.5 Electrochem.
Commun.
2015, 60, 13-16.
P3-Na0.5Li0.5Ni1/3Co1/3Mn1/3O2 17 74.85% 201.3 89.8/30th 2.0-4.6 J. Nanosci.
Nanotechnol. 16,
10698–10701,
2016
P2-Na0.85Li0.17Ni0.21Mn0.64O2 15 80% 112 95/50th 2.0-4.2 Adv. Energy
Mater. 2011, 1,
33-336
Zn-doped P2-
Na0.66Ni0.26Zn0.07Mn0.67O2
12 94% 150 118/30th 2.0-4.4 J. Power Sources
2015, 281, 18-26.
Mg doped P2-
Na0.67Mn0.67Ni0.28Mg0.05O2
17.3 94.6% 126.8 104.5/50th 2.5-4.35 Angew. Chem.
Int. Ed. 2016, 55,
1-6
P2-Na2/3(Mn1/2Fe1/4Co1/4)O2 25.8 89.3% 168 130/30th 1.5-4.2 Adv. Energy
Mater. 2015, 5,
1500944
3
P2-Na0.67Mn0.65Co0.2Ni0.15O2 20 >100% N/A 123/50th 2.0-4.4 J. Mater. Chem.
A 2013, 1(12):
3895.
P2-Nax(Fe1/2Mn1/2)O2 N/A >100% 121.3 101.4/80th 1.5-4.2 Chem. Mater.
2015, 27,
3150−3158
P2/O3-Na0.8Li0.2Ni0.5Mn0.5O2 15 >100% 130 128/20th 2.0-4.05 Adv. Energy
Mater. 2014, 4,
1400458
P2 Na0.67Ni0.33Mn0.67O2 17 >100% 130 40/100th 2.0-4.5 Electrochim.
Acta 2013, 113,
200-204
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Williamson-Hall analysis (http://pd.chem.ucl.ac.uk/pdnn/peaks/sizedet.htm)
This method is attributed to G.K.Williamson and his student, W.H.Hall (Acta
Metall. 1, 22-31 (1953)). It relies on the principle that the approximate formulae for
size broadening, βL, and strain broadening, βe, vary quite differently with respect to
Bragg angle, θ:
βL = Kλ/(L cosθ) Equation (1)
βe = Cε tanθ Equation (2)
One contribution varies as 1/cosθ and the other as tanθ. If both contributions are
present then their combined effect should be determined by convolution. The
simplification of Williamson and Hall is to assume the convolution is either a simple
sum or sum of squares. Using the former of these then we get:
βtot = βe + βL = Cε tanθ + Kλ/(L cosθ) Equation (3)
If we multiply Equation (3) by cosθ we get:
βtot cosθ = Cε sinθ + Kλ/L Equation (4)
and comparing this to the standard equation for a straight line (m = slope; c =
intercept)
y = mx + c
we see that by plotting βtotcosθ versus sinθ we obtain the strain component from the
slope (Cε) and the size component from the intercept (Kλ/L).
The Williamson-Hall method has many assumptions: its absolute values should
not be taken too seriously but it can be a useful method if used in the relative sense;
for example a study of many powder patterns of the same chemical compound, but
synthesized under different conditions, might reveal trends in the crystallite size/strain
which in turn can be related to the properties of the product.
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1 2 3 4 5 6 7
NCM-WQ NCM-600 NCM-Q
2-Theta, degree
Inte
nsity
, a.u
.
Figure S1 Synchrotron HEXRD patterns of NCM-Q, NCM-WQ and NCM-600.
6
NaO
Ni
C
MnCo
a b c
d e f
g h i
Figure S2 SEM images of the oxalate precursor (a-c) and the corresponding
elemental mapping (d-i).
7
a
2 4 6 8 10
CoMnNiCoNiNa
CoNi
NiCoMn
Inte
nsity
, cou
nts
Energy, keV
Mn
Ob
Figure S3 SEM image (a) and EDX analysis (b) of NCM-Q.
8
a b c
d e f
Na O
Co MnNi
Figure S4 SEM images of NCM-Q and the corresponding elemental mapping.
9
Figure S5 Fitting on the diffraction peak of NCM-Q (a, b), NCM-WQ (c, d) and
NCM-600 (e, f) before and after charged to 4.4 V using CMPR software.
10
1.15 1.20 1.25 1.30 2.4 2.6 2.8 3.0 3.2 3.4 3.6
P2(0
02)
P2(-1
13)
O3(
-114
)
O1(
-202
)
P2(0
12)
O3(
012)
P2(0
10)
O3(
-111
)
O3(
00-6
)O
1(00
2)P2
(004
)
P2(0
06)
P2(0
06)In
tens
ity, a
.u.
O1(
001)
P2(0
02)
O3(
003)
O3(
003)
P2/O1/O3_Pristine P2/O1/O3_0.5C for 100 cycles
2-Theta, degree
1 2 3 4 5 6 7
Pristine After 100 [email protected]
Inte
nsity
, a.u
.
2-Theta, degree
a
b
Figure S6 Full (a) and zoomed (b) synchrotron HEXRD patterns of pristine NCM-Q
electrode and after cycled at 0.5 C for 100 cycles.
11
0 5 10 15 20 25 30 35 40 45 50 55 60 650
40
80
120
160
200 Charge Discharge
Capa
city,
mAh
g-1
Cycle number
2-3.8V, 0.1C
Figure S7 Cycle performance of NCM-Q electrode at 0.1 C within 2.0-3.8 V.
12
0 10 20 30 40 500
200
400
600
800
Ener
gy D
ensit
y, W
h K
g-1
Cycle number
46 W kg-1, 2.0-4.4 V
a
0 500 1000 1500 20000
100
200
300
400
500
600
Ener
gy D
ensit
y, W
h kg
-1
Specific power, W kg-1
b
Figure S8 a) Energy density and b) power density of NCM-Q.
13
Figure S9 HEXRD patterns of deep-charged NCM-Q, NCM-WQ and NCM-600
(4.4V).
14
8330 8340 8350 8360 8370
0.0
0.5
1.0
1.5
2.0
Norm
alize
d Ab
sorp
tion
Inte
nsity
Energy, eV
Pristine C-4.4V D-2.0V
0 1 2 3 4 5 6
Ni-M
FT m
agni
tude
Radial distance (A)
Pristine C-4.4V D-2.0V
Ni-O
7710 7720 7730 7740
0.0
0.5
1.0
1.5
2.0
Norm
alize
d Ab
sorp
tion
Inte
nsity
Energy, eV
Pristine C-4.4V D-2.0V
0 1 2 3 4 5 6
Co-M
FT m
agni
tude
Radial distance (A)
Pristine C-4.4V D-2.0V
Co-O
6540 6550 6560 6570 6580
0.0
0.5
1.0
1.5
2.0
Norm
alize
d Ab
sorp
tion
Inte
nsity
Energy, eV
Pristine C-4.4V D-2.0V
0 1 2 3 4 5 6
Mn-M
FT m
agni
tude
Radial distance (A)
Pristine C-4.4V D-2.0V
Mn-O
o
a
c
e
b
d
f
Figure S10 Ex-situ XANES and EXAFS spectra of the NCM-WQ electrode at
different charge/discharge states: (a, d) Ni K-edge; (b, e) Co K-edge and (c, f) Mn K-
edge. C for charge and D for discharge.
15
8330 8340 8350 8360 8370
0.0
0.5
1.0
1.5
2.0
Norm
alize
d Ab
sorp
tion
Inte
nsity
Energy, eV
Pristine C-4.4V D-2.0V
6540 6550 6560 6570 6580
0.0
0.5
1.0
1.5
2.0
Norm
alize
d Ab
sorp
tion
Inte
nsity
Energy, eV
Pristine C-4.4V D-2.0V
0 1 2 3 4 5 6
FT m
agni
tude
Radial distance (A)
Pristine C-4.4V D-2.0V
0 1 2 3 4 5 6
FT m
agni
tude
Radial distance (A)
Pristine C-4.4V D-2.0V
7710 7720 7730 7740
0.0
0.5
1.0
1.5
2.0
Norm
alize
d Ab
sorp
tion
Inte
nsity
Energy, eV
Pristine C-4.4V D-2.0V
0 1 2 3 4 5 6
FT m
agni
tude
Radial distance (A)
Pristine C-4.4V D-2.0V
a
c
e
b
d
f
Figure S11 Ex-situ XANES and EXAFS spectra of the NCM-600 electrode at
different charge/discharge states: (a, d) Ni K-edge; (b, e) Co K-edge and (c, f) Mn K-
edge. C for charge and D for discharge.
16
8330 8340 8350 8360 8370
0.0
0.5
1.0
1.5
2.0
Norm
alize
d Ab
sorp
tion
Inte
nsity
Energy, eV
Pristine C-4.4V D-2.0V NiO
0 1 2 3 4 5 6
Ni-M Pristine C-4.4V D-2.0V
FT m
agni
tude
Radial distance (A)
Ni-O
8330 8340 8350 8360 8370
0.0
0.5
1.0
1.5
2.0
Norm
alize
d Ab
sorp
tion
Inte
nsity
Energy, eV
Pristine C-4.4V D-2.0V
0 1 2 3 4 5 6
Ni-M
FT m
agni
tude
Radial distance (A)
Pristine C-4.4V D-2.0V
Ni-O
8330 8340 8350 8360 8370
0.0
0.5
1.0
1.5
2.0
Norm
alize
d Ab
sorp
tion
Inte
nsity
Energy, eV
Pristine C-4.4V D-2.0V
0 1 2 3 4 5 6
Ni-O
FT m
agni
tude
Radial distance (A)
Pristine C-4.4V D-2.0V
Ni-M
a
c
e
b
d
f
Figure S12 Ex-situ Ni K-edge XANES and EXAFS for NCM-Q (a, b), NCM-WQ (c,
d) and NCM-600 (e, f) at different charge/discharge states. C for charge and D for
discharge.
17
1 2 3 4 5 6 7
Observed
Inte
nsity
, a.u
.
2-Theta, degree
Calculated Background Difference
0 10 20 30 40 50 60 70 80
2.0
2.5
3.0
3.5
4.0
4.5
5.0
Volta
ge, V
Time, h
15 mA g-1
a b
c
Figure S13 a) Rietveld refinement of HEXRD pattern and b) charge/discharge curves of LiNCM-333, c) in-situ HEXRD pattern of de-lithiated LiNCM-333 with the presence of 2 L electrolytes (1M LiPF6/EC+DMC).