Energy Storage Using Sodium-ion

Batteries (SIB)
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

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
2

Lithium & Sodium specifications

Categories

Li

Na

0.7

1.0

Cation radii

~ 7 g/mol

~ 23 g/mol

Molecular weight

0V

-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

* ~ 2% seawater is Na

http://minerals.usgs.gov/minerals/pubs/commodity/lithium/mcs-2011-sodaa.pdf

0
Year published
2014

2013

2012

2011

2010

2009

2008

2007

2006

2005

2004

2003

2002

2001

2000

1999

1998

1997

1996

1995

1994

1993

1992

1991

No. of publications
250

Na-ion batteries papers

200

150

100

50

Source- Web of science

4

Energy densities of battery technologies

Pb-acid

30-40

Ni-MH

45-60
100-110

LFP

150-190

LCO
NCA (Panasonic 18650)
Na-ion

240

140-150

Li/S

350
400

200

Li-metal (solid state)

under development
Li-O2 (air)
under development
0
50
100
150
Wh/kg

600
900
200

250

Source- C&ENews (July 2014)

55

Energy Density* range of Na-ion (3.0 V; pouch cell)

BatPaC# (ANL model) for storage applications
Cell Energy Density, Wh/kg

300
250

Na metal
Sodium
metal

4.0 V

NaxSn
NaxSnSb

200

(600 mAhg-1)

NaxC
mAh/g
NaxC250
250
mAh/g
NaxC
mAh/g
NaxC200
200
mAh/g

150

NaxC
mAh/g
NaxC100
100
mAh/g

100
50

Finished battery module:

conventional cell design

power/energy ratio = 2

0
80

100

120

140

160

180

200

220

CapacityofofNaCathode,
mAh/g
Capacity
yMnO2, mAh/g

*Energy density model : quite cell voltage dependent (4.0 V; ~30-40% )

# - http://www.cse.anl.gov/batpac/index.html

Eroglu et al., J. Power Sources, 267, 14 (2014)

6

4.4 V class Na-ion battery cathode

Na/Na4Co2.4Mn0.3Ni0.3(PO4)2P2O7

b
a

Argonne BatPaC Model - ED -> 275 300 Whkg-1 (NaxSnSb anode)

Nose
e
Nose et al., Electrochem. Commun, 34, 266 (2013)

7
7

SnO_C nanocomposite anode material

Intensity

SnO after ball milling

pristine SnO

10

20

30

40

50

2 Theta (degrees)

60

70
8

SnO_C conversion anode (~740 mAhg-1)

120

1st cycle
2nd cycle

60%
60%
active
active
C/5 (100 mAg-1)

charge
discharge

600

100

2.0

Voltage(V)

80

-1

Capacity (mAh g )

2.5

1.5

1.0

400
60

40
200
20

0.5
0
0

0.0
0

100

200

300

400

500

600

700

10

15

20

25

30

0
35

Cycle number

Capacity(mAh g-1)

Efficiency

3.0

SnO_C cell rate

1400
Relative capacity

1.0

Capacity (mAh g-1)

1200
1000
800

0.8
0.6
0.4

relative discharge capacity

0.2

charge capacity
discharge capacity

0.0

100

1000

Applied current (mA/g)

600

C/10

C/5

C/10

C/2

400

2C

5C

200
0
0

10

20

30

40

50

60

70

Cycle number

Dual amorphous buffer carbon & sodia matrix

10

Na||SnO_C operando HEXRD

70
60

Time (h)

Offset Y values

50
40
30
20
10

SnO
2.0

0
2.5

3.0

3.5

2 theta (degrees)

4.0

Voltage (V)

SnO decomposes to amorphous phase

11

XANES result of cycled NaySnO_C

Sn K edge

peak energy (eV)

29201.5

pristine SnO

SnO charged back to 3 V

29201.0

29200.5

SnO discharged to 0.4 V

Sn atom
accepting
charge

SnO discharged to 0.25 V

Sn foil

29200.0

SnO discharged to 0.005 V

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

x in NaxSnO

Amorphous intermetallic formed with Sn as Zintl anion

12

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
13

Hard carbon electrochemical performance

superior cycling stability

observed
23Na NMR analysis in
progress
5 mV 1.5 V
14

Na diffusion in O- vs. P-type layered compounds

MO6

Diffusion thru facesharing tetrahedral sites

High energy barrier

Na
MO6

Octahedral
Diffusion thru facesharing another trigonal
prismatic sites
Low
energy barrier

Prismatic


P2 less Na than O3 structure in as-prepared state

 Na/M < 1
15

P3, P2/P3, and P2 Na TM layered oxide materials:

NaxNi0.25Mn0.75O2
15000

Na0.7Ni0.25Mn0.75O2
Na0.6Ni0.25Mn0.75O2
Na0.5Ni0.25Mn0.75O2

P3

2theta (1)

10000

P2

P2/P3
5000

P2

P3

0
10

20

30

40

50

60

70

EJ22295 (BANK)

16

Electrochemical Na-(de)intercalation
Mn
4

0.002

(b)

P2/P3

(c)

P3

-0.002
0.006

4
3

Na0.6Ni0.25Mn0.75O2

dQ/dV

Voltage (V vs. Na)

P2

0.000

Na0.7Ni0.25Mn0.75O2

(a)

0.003
0.000
-0.003
0.006

0.003

3
Na0.5Ni0.25Mn0.75O2

0.000
-0.003

50

100

150

200

1.5

2.0

Specific capacity (mAh/g)

Weak charge ordering

Mn redox occurring

2.5

3.0

3.5

4.0

Voltage (V vs. Na)

17

Structure schematic: Na1.0Li0.2Ni0.25Mn0.75Oy

Na0.85Li0.17NiII0.21MnIV0.64O2
Li, Ni, Mn

Na

B
A

Na 1.02
Li 0.76
Ni2+ - 0.69
Mn4+ - 0.53
cycle Na into and out of host
Li reversibly moves inside host
TM<->Na layer (Oh/Td) *

P2 structure
D. Kim et al., Adv. Energy Mater. 1, 333 (2011)
*J. Xu, S. Meng et al., Chem. Mater. (2013)

18

Rietveld refinement (HEXRD): Na0.85Li0.17Ni0.21Mn0.64O2

P63/mmc
a = 2.879232(8)
c = 11.06584(6)




Superstructure peaks (Li/Ni(II)/Mn(IV) motif)

Slight Li2MnO3 impurity
N. Karan, M. Slater et al., J. Electrochem. Soc, 161, A1107 (2014)

19

Changes During Cycling

As prepared:
Na1.08Li0.22Ni0.25Mn0.75Oy
Charged to 4.2 V:
Na0.54Li0.19Ni0.23Mn0.75Oy

Unit-cell volume contracts by

0.6% on charging to 4.2 V

Kim, et al., Adv. Energy Mat., 2011

20

Operando X-ray Absorption (XAS)

Na/Na0.85Li0.17Ni0.21Mn0.64O2
cell operation

4.5

4.0

C7

C8

XANES

C6
C5

C4
C3

3.0

C1

C2

2.5
0

20

40

60

80

100

Capacity (mAh/g)
4.0

(a)

laminate_AP
C1
C2
C3
C4
C5
C6
C7
C8

Mn

first in-situ discharge

Normalized XANES (a.u)

3.5

Normalized XANES (a.u)

Potential (vs. Na /Na)

first in-situ charge

6530

6540

6550

6560

Mn

6570

6530

Photon energy (eV)

Normalized XANEX (a.u)

D1
D2

3.0

D3
D4

2.5

D5

2.0

D6

10

20

30

40

50

Capacity (mAh/g)

60

6550

6560

6570

(b)

laminate_AP
C1
C2
C3
C4
C5
C6
C7
C8

Ni

70

6540

Photon energy (eV)

8330

8340

8350

8360

Photon energy (eV)

Normalized XANEX (a.u)

3.5

Potential (vs. Na /Na)

-10

(c)
laminate_AP
before dis (fully ch)
D1
D2
D3
D4
D5
D6

8370

(d)

laminate_AP
before dis (fully ch)
d1
D2
D3
D4
D5
D5

Ni

0
8330

8340

8350

8360

8370

Photon energy (eV)

N. Karan, M. Slater et al., J. Electrochem. Soc, 161, A1107 (2014)

21

Cycling performance Na/Na0.85Li0.17Ni0.21Mn0.64O2

half cell
140

Cycle Profile
MS52c13
P2-Layered Na
Li
Ni
0.85 0.17 0.21Mn0.64O2

1.0

120
100
0.6

80

25C

60

0.4

C/24 charge, 118 mAh/g

(within ~5% theoretical)

40

0.2

Charge
Discharge
Efficiency

20
0
0

10

Efficiency

Specific Capacity (mAh/g)

0.8

20

30

40

0.0
50

Cycle#
Kim, et al., Adv. Energy Mat., (2011)

22

15

20

30

35

40

45

50

x in Na1-xLixNi0.5Mn0.5Oy

Li-O3
Na-P2

x=
1.0
0.95
0.9
0.7
0.5
0.3
0.2
0.1
0.05
0

Na-O3

Li-O3 (015)

Li-O3 (104)

Li-O3 (012)

Na-O3 (012)

Li-O3 (101)

Na-O3 (101)

Na-O3 (006)

Li-O3 (003)

Na-O3 (003)

Intensity (a.u.)

Na-P2 (003)

Capacity boost 25% Ni -> 50% content Ni using

Na1-xLixNi0.5Mn0.5Oy (effect on phase distributions)

55

2Theta (degree, CuK)

 Upon Li substitution, Na-O3 phase is gradually replaced by Na-P2 phase, and NaP2 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.
E. Lee et al., Adv. Energy Mater. (2014) 23

Electrochemical performance of Na1-xLixNi0.5Mn0.5Oy

100

140

15 mA/g

100

30 mA/g
75 mA/g

80

150 mA/g

x=0
x=0.05
x=0.1
x=0.2
x=0.3

60
40
20
0

Relative capacity (%)

Capacity (mAh/g)

120

10

x=0.2
80

x=0.1

70

x=0.05

60
50

12

x=0.3

90

x=0

30

Cycle number

4.5

4.5

120

150

180

Na0.7Li0.3Ni0.5Mn0.5Oy

4.0

3.5

Voltage, V

Voltage, V

90

Current density (mA/g)

NaNi0.5Mn0.5Oy

4.0

60

3.0
2.5
2.0

3.5
3.0
2.5

Charge 1
Discharge 1
Charge 2
Discharge 2

2.0

1.5

1.5
0

30

60

90

120

Capacity, mAh/g

150

180

30

60

90

120

150

180

Capacity, mAh/g
E. Lee et al., Adv. Energy Mater. (2014)

24

O3 to P2 conversion is unfavorable process

A B C A B C

BCABCA
ABCABC

O3

ABCABC
BCABCA
BCABCA
ABCABC

TM-O bond
breaking:
unfavorable

B C A B C A

Unit cell

B C A B C A
A B C A B C
A B C A B C

P2

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
25

Operando synchrotron HEXRD of Na0.7Li0.3Ni0.5Mn0.5Oy

Initial cycle

P2-(006)

P3-(015)

P2-(012)

P3-(012)

P3(006)

P3(101)

1200

1000

(d) P2/P3

600

(c) P2/O''3
400

Beam interrupted
Beam interrupted

Time (min)

Intensity (a.u.)

800

Beam interrupted

(b) P2/P3
200
(a) P2/{O3}

O3

O3

O3
O3-(014)

17

18

19

20

2 ( = 0.0765 nm)

21

22

23

24

Voltage (V)

E. Lee et al., Adv. Energy Mater. (2014)

26

Na containing
phase

O3

P3

layer glide
Yellow sphere
Na
Na/Li containing
phase

P2

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
E. Lee et al., Adv. Energy Mater. (2014)

27

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

Na-ion intermetallic alloy anodes and hard carbon:

Dehua Zhou1
Maryam Peer5
Michael Slater1
Na-ion layered transition metal oxides:
Eungje Lee1
Stephen Hackney4
1Chemical Sciences and Engineering Division
Donghan Kim1
Aaron DeWahl4
2Advanced Photon Source
Sun-Ho Kang1
3Electron Microscopy Center
Michael Slater 1
BatPaC
4Michigan Technological University
Jun Lu1
Kevin Gallagher1
5Penn State University
Dean Miller3
Paul Nelson1
Jianguo Wen3
Naba Karan2
M. Balasubramanian2
This LDRD work @ Argonne was supported by the U. S.
Yang Ren2
Department of Energy, US DOE-BES, under Contract No. DEXiangyi Luo2
AC02-06CH11357
Xiaoyi Zhang3

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.
29