Christopher S. Johnson
Dehua Zhou, Eungje Lee, Michael Slater
Chemical Sciences and Engineering Division
Argonne National Laboratory U.S.A.
Beyond Li-ion Batteries VIII Conference
Oak Ridge National Laboratory TN, 2-4 June 2015
Energy Storage Using Sodium-ionBatteries (SIB)
22
Why Na-ion batteries?
• Revisit the system -> leverage knowledge from Li-ion
• Room for big improvements and understanding in Na are possible
• Motivating factor-> nice potential for low-cost
• May provide a quasi-backup technology to Li-ion or drop-in
replacement
Al current collectors
Many known Na inorganic compounds
Lower voltage – longer stability
Solid-state electrolytes - proven
33
Categories
0.7 Å 1.0 Å Cation radii
~ 7 g/mol ~ 23 g/mol Molecular weight
0 V -0.3 V E0 (vs. Li/Li+)
$5000/ton $150/ton×××× Cost - carbonates
3829 mAh/g 1165 mAh/g Capacity (mAh/g) - metal
Octahedral and tetrahedral
Octahedral and prismatic
Coordination preference
Li
Lithium & Sodium – specifications
Na
×http://minerals.usgs.gov/minerals/pubs/commodity/lithium/mcs-2011-sodaa.pdf
* ~ 2% seawater is Na
4
“Na-ion batteries” papers
Source- Web of science
1992
1993
1994
1995
1996
1997
1998
1999
2000
2001
2002
2003
2004
2006
2005
2007
2008
2009
2010
2011
2012
2013
2014
1991
0
50
100
150
200
250N
o. o
f p
ub
licat
ion
s
Year published
55
Energy densities of battery technologies
5
Pb-acid
Ni-MH
LFP
LCO
NCA (Panasonic 18650)
Na-ion
Li/S
Li-metal (solid state)under development
Li-O2 (air)under development
0 50 100 150 200 250Wh/kg
600
900
140-150
240
200
150-190
100-110
45-60
30-40
400
Source- C&ENews (July 2014)
350
6
0
50
100
150
200
250
300
80 100 120 140 160 180 200 220
Capacity of NayMnO2, mAh/g
Cel
l En
ergy
Den
sity
, Wh
/kg
Sodium metal
NaxSn
NaxC 250 mAh/g
NaxC 200 mAh/g
NaxC 100 mAh/g
Na metal
NaxSnSb (600 mAhg-1) NaxC 250 mAh/g
NaxC 200 mAh/g
NaxC 100 mAh/g
Capacity of Cathode, mAh/g
power/energy ratio = 2
Energy Density* range of Na-ion (3.0 V; pouch cell) BatPaC# (ANL model) for storage applications
# - http://www.cse.anl.gov/batpac/index.html
*Energy density model : quite cell voltage dependent (4.0 V; ~30-40% ↑)◊
• Finished battery module:
conventional cell design
◊ Eroglu et al., J. Power Sources, 267, 14 (2014)
4.0 V
7
4.4 V class Na-ion battery cathode
7Nose e
Na/Na4Co2.4Mn0.3Ni0.3(PO4)2P2O7
Argonne BatPaC Model - ED -> 275 – 300 Whkg-1 (NaxSnSb anode)
Nose et al., Electrochem. Commun, 34, 266 (2013)7
b
a
SnO_C nanocomposite anode material
8
10 20 30 40 50 60 70
SnO after ball milling
In
ten
sit
y
2 Theta (degrees)
pristine SnO
60% active
99
SnO_C conversion anode (~740 mAhg-1)
0 100 200 300 400 500 600 700
0.0
0.5
1.0
1.5
2.0
2.5
3.0
Vo
lta
ge
(V)
Capacity(mAh g-1)
1st cycle
2nd cycle
0 5 10 15 20 25 30 350
200
400
600
charge
discharge
Cap
acit
y (
mA
h g
-1)
0
20
40
60
80
100
120
Eff
icie
ncy
Cycle number
60% active
C/5 (100 mAg-1)
SnO_C cell rate
10
0 10 20 30 40 50 60 700
200
400
600
800
1000
1200
1400
100 10000.0
0.2
0.4
0.6
0.8
1.0
charge capacity discharge capacity
Cap
acity
(m
Ah
g-1)
Cycle number
0 10 20 30 40 50 60 70
C/10C/5 C/2 C 2C
5C
C/10
relative discharge capacity
Rela
tive
cap
acit
y
Applied current (mA/g)
• Dual amorphous buffer – carbon & sodia matrix
Na||SnO_C operando HEXRD
11
2 1 02.0 2.5 3.0 3.5 4.0
Voltage (V)
0
10
20
30
40
50
60
70
Tim
e (
h)
Off
se
t Y
va
lue
s
2 theta (degrees)
SnO
• SnO decomposes to amorphous phase
1212
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
29200.0
29200.5
29201.0
29201.5
SnO discharged to 0.005 V
SnO discharged to 0.25 V
pe
ak e
nerg
y (e
V)
x in NaxSnO
pristine SnO
SnO charged back to 3 V
SnO discharged to 0.4 V
XANES result of cycled NaySnO_CSn K edge
Sn atom
accepting
charge Sn foil
• Amorphous intermetallic formed with Sn as Zintl anion
13
Spherical hard carbon
• polymer precursor pyrolysis method
• 0.2 to 0.6 micron spheres
• graphene sheets interlayer distance is 0.4 nm
• I(D)/I(G) ratio is 1.04
• BET is 480 m2 g-1
• Cumulative pore volume is 0.164 cm3 g-1
Hard carbon electrochemical performance
14
• superior cycling stability
observed
• 23Na NMR analysis in
progress5 mV – 1.5 V
1515
Na diffusion in O- vs. P-type layered compounds
Na
MO6
MO6
Octahedral
Diffusion thru face-
sharing tetrahedral sites
���� High energy barrier
Prismatic
Diffusion thru face-
sharing another trigonal
prismatic sites ���� Low
energy barrier
� P2 – less Na than O3 structure in as-prepared state
� Na/M < 1
16
P3, P2/P3, and P2 Na TM layered oxide materials:NaxNi0.25Mn0.75O2
10 20 30 40 50 60 700
5000
10000
15000
2the
ta (
1)
EJ22295 (BANK)
Na0.7Ni0.25Mn0.75O2 Na0.6Ni0.25Mn0.75O2 Na0.5Ni0.25Mn0.75O2
P3
P2/P3
P2
P2
P3
17
Electrochemical Na-(de)intercalation
2
3
4
2
3
4
0 50 100 150 200
2
3
4
Na0.7Ni0.25Mn0.75O2
Na0.6Ni0.25Mn0.75O2
Vol
tage
(V
vs.
Na)
Na0.5Ni0.25Mn0.75O2
Specific capacity (mAh/g)
-0.002
0.000
0.002
-0.003
0.000
0.003
0.006
1.5 2.0 2.5 3.0 3.5 4.0
-0.003
0.000
0.003
0.006
(a) P2
P2/P3(b)
dQ/d
V
P3(c)
Voltage (V vs. Na)
• Weak charge ordering
• Mn redox occurring
Mn
18
A
A
B
B
Na
Li, Ni, Mn
Na – 1.02 ǺLi – 0.76 ǺNi2+ - 0.69 ǺMn4+ - 0.53 Å
cycle Na into and out of hostLi reversibly moves inside hostTM<->Na layer (Oh/Td) *
Structure schematic: Na1.0Li0.2Ni0.25Mn0.75Oy
Na0.85Li0.17NiII0.21MnIV0.64O2
D. Kim et al., Adv. Energy Mater. 1, 333 (2011)
*J. Xu, S. Meng et al., Chem. Mater. (2013)
P2 structure
Rietveld refinement (HEXRD): Na0.85Li0.17Ni0.21Mn0.64O2
19N. Karan, M. Slater et al., J. Electrochem. Soc, 161, A1107 (2014)
� Superstructure peaks (Li/Ni(II)/Mn(IV) motif)
� Slight Li2MnO3 impurity
a = 2.879232(8)
c = 11.06584(6)
P63/mmc
20
Changes During Cycling
� Unit-cell volume contracts by 0.6% on charging to 4.2 V
As prepared:
Na1.08Li0.22Ni0.25Mn0.75Oy
Charged to 4.2 V:Na0.54Li0.19Ni0.23Mn0.75Oy
Kim, et al., Adv. Energy Mat., 2011
21
Operando X-ray Absorption (XAS)Na/Na0.85Li0.17Ni0.21Mn0.64O2
cell operation
21
0 20 40 60 80 1002.5
3.0
3.5
4.0
4.5
Pot
entia
l (vs
. Na+
/Na)
Capacity (mAh/g)
first in-situ charge
C1C2
C3
C4
C5
C6
C7C8
-10 0 10 20 30 40 50 60 70
2.0
2.5
3.0
3.5
4.0
first in-situ discharge
Capacity (mAh/g)
Pot
entia
l (vs
. Na+
/Na)
D1
D2
D3
D4
D5
D6
6530 6540 6550 6560 6570
0
1
2
laminate_AP C1 C2 C3 C4 C5 C6 C7 C8
N
orm
alized
XA
NE
S (
a.u
)
Photon energy (eV)
(a)
8330 8340 8350 8360 83700
1
2
laminate_AP C1 C2 C3 C4 C5 C6 C7 C8
No
rmalized
XA
NE
X (
a.u
)
Photon energy (eV)
(b)
8330 8340 8350 8360 83700
1
2
laminate_AP before dis (fully ch) d1 D2 D3 D4 D5 D5
No
rmalized
XA
NE
X (
a.u
)
Photon energy (eV)
(d)
6530 6540 6550 6560 6570
0
1
2
laminate_AP before dis (fully ch) D1 D2 D3 D4 D5 D6
N
orm
alized
XA
NE
S (
a.u
)
Photon energy (eV)
(c)
N. Karan, M. Slater et al., J. Electrochem. Soc, 161, A1107 (2014)
XANES
Mn Mn
NiNi
C/24 charge, 118 mAh/g (within ~5% theoretical)
22
0 10 20 30 40 500
20
40
60
80
100
120
140
Charge Discharge Efficiency
Cycle Profile MS52c13
Spe
cific
Cap
acity
(m
Ah/
g)
Cycle#
0.0
0.2
0.4
0.6
0.8
1.0
Effi
cien
cy
Cycling performance – Na/Na0.85Li0.17Ni0.21Mn0.64O2
half cell
25C
Kim, et al., Adv. Energy Mat., (2011)
P2-Layered Na0.85Li0.17Ni0.21Mn0.64O2
23
15 20 30 35 40 45 50 55
Li-
O3 (
003)
Na-O
3 (
003)
Inte
nsity
(a.
u.)
Na-P
2 (
003)
Na-O
3 (
012)
Li-
O3 (
012)
Li-
O3 (
101)
Na-O
3 (
101)
Na-O
3 (
006)
Li-
O3 (
015)Li-
O3 (
104)
x =
1.0
0.95
0.9
0.7
0.5
0.3
0.2
0.1
0.05
2Theta (degree, CuKα)
0
Capacity boost 25% Ni -> 50% content Ni using Na1-xLixNi0.5Mn0.5Oy (effect on phase distributions)
23
� Upon Li substitution, Na-O3 phase is gradually replaced by Na-P2 phase, and Na-
P2 by Li-O3
� The presence of P2 structure, which normally forms at low Na/TM ratio, implies
the possible formation of lithium rich layered phase and Ni-Mn ratio offset in
the rest of Na phases.
Na-
O3
Na-
P2
Li-O
3x
in
N
a1
-xLi
xNi 0
.5M
n0
.5O
y
E. Lee et al., Adv. Energy Mater. (2014)
2424E. Lee et al., Adv. Energy Mater. (2014)
1.5
2.0
2.5
3.0
3.5
4.0
4.5
0 30 60 90 120 150 180
Voltage, V
Capacity, mAh/g
Charge 1
Discharge 1
Charge 2
Discharge 21.5
2.0
2.5
3.0
3.5
4.0
4.5
0 30 60 90 120 150 180
Voltage, V
Capacity, mAh/g
Electrochemical performance of Na1-xLixNi0.5Mn0.5Oy
NaNi0.5Mn0.5Oy Na0.7Li0.3Ni0.5Mn0.5Oy
0 2 4 6 8 10 120
20
40
60
80
100
120
140
150 mA/g
75 mA/g
30 mA/g
Cap
acity
(m
Ah/
g)
Cycle number
x=0 x=0.05 x=0.1 x=0.2 x=0.3
15 mA/g
0 30 60 90 120 150 18050
60
70
80
90
100
x=0
x=0.05
x=0.1
x=0.2
Rel
ativ
e ca
paci
ty (
%)
Current density (mA/g)
x=0.3
25
O3 to P2 conversion is unfavorable process
A B C A B C
B C A B C A
B C A B C A
A B C A B C
A B C A B C
B C A B C A
B C A B C A
A B C A B C
P2Unit cell
O3
TM-O bond
breaking:
unfavorable
B C A B C A
A B C A B C
A B C A B C
B C A B C A
B C A B C A
A B C A B C
• Need to synthetically incorporate P2 in composite
to improve echem performance
26
2 3 4
0
200
400
600
800
1000
1200
(d)
(b)
(c)
P2/P3
P2/P3
P2/O''3
Tim
e (m
in)
Voltage (V)
P2/{O3}
Initial cycle
(a)
8 9
P3(0
06)
Beam interrupted
Inte
nsity
(a.
u.)
17 18 19 20 21 22 23 24
O3-(014)
P3-(
01
5)
P3-(
012)
P3(1
01
)
Beam interrupted
P2
-(006)
P2-(
012
)
2θ (λ = 0.0765 nm)
Beam interrupted
Operando synchrotron HEXRD of Na0.7Li0.3Ni0.5Mn0.5Oy
E. Lee et al., Adv. Energy Mater. (2014)
O3 O3 O3
27E. Lee et al., Adv. Energy Mater. (2014)
• O3/P2 Intergrowth (pristine)
• Li presence assists in P2 formation
• P3 formed from O3 (aligns w/P2)
• P2 phase remains and acts
like a ‘glue’
O3
P2
Yellow sphere
Na
Na/Li containing
phase
↑Na containing
phase
layer glide
P3
Thoughts, Summary and Conclusions
• Na-ion batteries are an emerging energy storage technology
• The battery work presented herein encompassed:
– High-capacity SnO_C anodes
• Amorphous intermetallics
– Long-life Hard carbon anodes
– 1000 cycles @ 1C rates
– Bulk mixed-metal layered oxide cathodes
• Li-containing systems
– Flexible and inter-block stacking arrangements• P2 importance
• Energy density more tied to cell voltage
– New materials needed• Anodes with lower voltages & high capacities
• Raise cathode reaction voltage
28
29
Na-ion intermetallic alloy anodes and hard carbon:
Dehua Zhou1
Maryam Peer5
Michael Slater1
Na-ion layered transition metal oxides:
Eungje Lee1 Stephen Hackney4
Donghan Kim1 Aaron DeWahl4
Sun-Ho Kang1
Michael Slater1
Jun Lu1
Dean Miller3
Jianguo Wen3
Naba Karan2
M. Balasubramanian2
Yang Ren2
Xiangyi Luo2
Xiaoyi Zhang3
1Chemical Sciences and Engineering Division2Advanced Photon Source3Electron Microscopy Center4Michigan Technological University5Penn State University
• This LDRD work @ Argonne was supported by the U. S.
Department of Energy, US DOE-BES, under Contract No. DE-
AC02-06CH11357
• Use of the Center for Nanoscale Materials, The Advanced Photon
Source, and the Electron Microscopy Center is supported by the
U. S. Department of Energy, Office of Science, Office of Basic
Energy Sciences, under Contract No. DE-AC02-06CH11357.
BatPaC
Kevin Gallagher1
Paul Nelson1
