Page 1

Ionic Liquid-based Electrolytes for Next Generation Batteries

Stefano Passerini
University of Muenster, Institute of Physical Chemistry, Corrensstr. 28/30 Muenster
Germany
Beyond Lithium Ion, June 5, 2012
Muenster
Electrochemical
Energy
Technology
Research Groups:
Prof. Martin Winter
Prof. Stefano Passerini
Young Researcher Groups:
Dr. Alexandra Lex-Balducci (2009 -)
Dr. Andrea Balducci (2009 -)
Dr. Jie Li (2012 -)
50 Ph.D. Students
30 Scientists with Ph.D.
10 Bachelor Students
Ionic Conductivity in IL-based Materials for
Energy Storage
Liquid electrolytes
Ionic Conductivity in IL-based Materials for
Energy Storage
Polymer electrolytes
Li Ion Batteries Initiated a Technical Revolution....
and might be ready for more
2005 1990 by Sony Market Introduction
medium
0.7Bio (2008)
7Bio (2008) Market Size
LEV, Power Tools
Consumer
Applications
Moderate Minimal
Chances for
Newcomers
Realization has
to be proven
Very large
Stationary Elec.
Storage
Depends on
starting position
100 10.000 0.1 1 0.001 0.1
Typ. Battery-Size
(kWh)
2012/15
(mostly HEV)
large
25Bio (2020)
Automotive
HEV & EV
(Very) Good
1 100
Conductivity
Vapor pressure
Environment - friendly
Film forming ability (SEI)
Electrochemical stability window
Temperature range of use
Electrolyte System
State of the art:
Organic solvent-based electrolytes
LiPF
6
, EC, DEC, additives
Key-role of Electrolyte in Li-Ion Batteries
S
e
p
a
r
a
t
o
r
SEI
N
e
g
.

C
u
r
r
e
n
t

C
o
l
l
e
c
t
o
r

(
C
u
)
P
o
s
.

C
u
r
r
e
n
t

C
o
l
l
e
c
t
o
r

(
A
l
)
Anode Cathode
Electrolyte
Li-Ion cells: Role of the SEI film
However ..
Safety of present Li-ion cells is still an open issue
Li
x
C
6
+ Li
y
MO
z
C
6
+ Li
(y+x)
MO
z
Cu Graphite SEI org. Electrolyte Film Cathode Al
Li
+
X
-
" Full"
" Empty"
Or
" Empty"
Li
x
C
6
Li
+
Li
+
Li
y
MO
z
Towards Safer Batteries:
What do we learn from LIBs?
Key Step Forward: Replacement of volatile, flammable and
electrochemically unstable electrolyte components
Room temperature molten salts (Ionic Liquids)
PYR
14
FSI
Ionic Liquid-based
Electrolyte
butyl conformations found in
various crystal structures
well-know flexibility of the TFSI
-
anion
between 2 low-energy conformations
Ion Conformational Changes
Weak interactions due to large cation and anion
delocalization and low tendency to crystallize due to
flexibility (anion) and dissymmetry (cation)
Ionic Liquids Low Temperature Melting Salts
Salts, or mixtures of salts (composed solely of ions), which are liquid
at low temperatures (<100C) often below RT
0 sec
ORGANIC ELECTROLYTE IONIC LIQUID ELECTROLYTE
0 sec
2 sec
3 sec
Flammability: Organic electrolyte vs. Ionic
Liquids
Ionic Liquids (IL, RTIL, RTMS, etc.)
Properties
Wide electrochemical window
Wide liquid range
Very low volatility at ambient
pressure
Good thermal stability
High ionicity
Co-salts for
solid-state
polymer electrolytes
Solvents for
liquid electrolytes
Thousands of possible ILs available
PYR
13
TFSI ionic
liquid
Impurities: <100 ppm
Water: <10 ppm
Clear, uncolored
G.B Appetecchi et al., J ES 153(9) (2006) A1685.
Synthesis of Ionic Liquids
N
I
-
+
N
I
+
ethyl acetate
filtration
N
TFSI
-
+
LiTFSI aq.
phase separ.
purification
AC & Al
2
O
3
Li = lithium
PYR
1A
= N-alkyl-N-methylpyrrolidinium
TFSI = bis(trifluoromethanesulfonyl)imide, (CF
3
SO
2
)
2
N
-
FSI = bis(fluorosulfonyl)imide, (FSO
2
)
2
N
-
Boosting Performance
Combining Ionic Liquids
PYR
13
FSI (m.p. -10C) - PYR
14
TFSI (m.p. -5C)
Mixtures have much lower
melting temperatures than
constituent Ionic Liquids
due to additional ion
mismatching
Castiglione et al. J PC B113, 10750 (2009), Zhou et al. J PC C 114, 6201 (2010), Kunze et al. J PC C 114, 12364 (2010)
Are ionic liquids capable of dissolving Li salts?
PYR
13
TFSI - LiTFSI
Yes, but only at low Li concentration because new crystalline phases are
formed for high Li content
Hendersonetal.Chem.Mater.16,2881(2004)
Aggregation of Pyr
1N
TFSI ILs (NMR, Raman)
N
+
C H
3
CH
3
N
+
C H
3
CH
3
Pyr
13
+
Pyr
18
+
Pyr
14
+
Pyr
15
+
Pyr
16
+
Pyr
17
+
N
-
S S
CF
3
CF
3
O
O
O
O
TFSI
polar&
chargedregion
nonpolar
region
chargecompensation
Pyr
TFSI

TFSI

TFSI

TFSI

variation of side
chain length
Pyr
1[2O1]
+
TFSI
variation of side
chain type
Pyr
1[2O2]
+
nonpolarsidechains polarsidechains
N
-
S S
CF
3
CF
3
O
O
O
O
N
+
C H
3
CH
3
N
+
C H
3
CH
3
N
-
S S
CF
3
CF
3
O
O
O
O
TFSI
Li
+
Effect of Li
+
cation
Local Motion in Ionic Liquids:
NMR characterization (Two Step Model)
et
s
>>1:
R
1
only influenced by fast bond rotations
in the molecule that take place during the
time t
f
not influenced by aggregation of
molecules
R
2
is largely influenced by the slow
reorientations and experiences the
molecular aggregation
( )
( )
2 2
2 2 2 2
2
2
1
1 1
f
s
s f
J S S
t
t
e
e t e t
= +
+ +
( )
( )
2
3cos 1
2
S
u
=
2
2 2
2 1
9
20
s
R R R S
t
_ t A = ~
Wennerstrm,H.,etal.J.Am.Chem.Soc. 101,68606864(1979)
spectraldensity:
t
f
characterizes the fast internal
motions (bond rotations)
t
s
describes rotational tumbling
of the molecule
spinlattice and spinspin relaxation of a
surfactant are sensitive to fast local
motions and slow motions, respectively
0
2
4
6
8
10
12
+LiTFSI +LiTFSI +LiTFSI
Pyr
14
TFSI Pyr
15
TFSI Pyr
16
TFSI

R

(
2
H
)

/

s
-
1
Pyr(x)TFSI
R
1
R
2
! R
Pyr
13
TFSI
+LiTFSI
0.00
0.05
0.10
! R/
NMR measurements: T1 and T2 vs x (in Pyr
1x
TFSI)
Typical behavior of micelles indicating the formation of aggregates
Aggregation in Pyr
1x
TFSI
R
1
independent on chain length
fast local motions not influenced
R
2
dependent on chain length
slow local motions influenced
two different linear dependences
different aggregation
mechanisms
In presence of Li
+
AR differs from 0
already for propyl chain
Li forces cation aggregation
Pyr
15
TFSI
Aggregation type?
Pyr
14
TFSI
increaseofthe
numberofcations
inanaggregate
increaseofthe
numberofcations
inanaggregate
Pyr
13
TFSI Pyr
16
TFSI Pyr
18
TFSI
increaseofaggregatesize
duetoincreasing
chainlength
Raman measurements
The aggregation is
confirmed by the shift of
characteristic Raman peaks
Aggregation in Pyr
1x
TFSI
Cation aggregation: Li
+
--- TFSI
-
ion-pairing
( )
n
inLi TFSI
n
+

increase of anions,
which surround the Li
+
@ 742 cm
-1
expansion and
contraction of the whole TFSI-anion
@ 748 cm
-1
damped TFSI-anion
expansion and contraction due to
Li
+
clustering
increase of mode @ 748 cm
-1
with
increasing side chain length
more anions are clustering the Li-
cation when more Pyr-cations
cluster with themselves
M. Kunze, et al., Adv. En. Mat. (2011) 1,1
LiTFSI LiTFSI
Li---TFSI
Li---TFSI
PYR
+
1x
aggregate formation in presence of Li
+
increase of the
number of cations
inanaggregate
increaseofthe
numberofcations
inanaggregate
increaseofaggregatesize
duetoincreasing
chainlength
Pyr
13
TFSI Pyr
14
TFSI Pyr
15
TFSI Pyr
16
TFSI Pyr
18
TFSI
Paillard et al., J ES 156, A891(2009) Zhou et al. J PC C 114, 6201 (2010)
Sub-ambient temperature
melting electrolytes
The electrolytic mixture
0.85 PY
14
FSI - 0.15 LiFSI
melts below -40C
The electrolytic mixtures with
x> 0.15 show only glass
transition below -60C
x LiFSI (1-x) PYR
14
FSI
Tailored electrolyte: Li salt in PYR
14
FSI
High ionic conductivity at
sub-ambient temperatures
Wide Electrochemical Stability
Window (ESW)
LiFSI PYR
14
FSI mixtures for electrolytes
ANODE: Li
4
Ti
5
O
12
(LTO)
CATHODE: LiFePO
4
(LFP)
BINDER: CMC
ELECTROLYTE: 0.1LiTFSI 0.9 PYR
14
FSI
ILLIBATT Prototype
Active material loading: 0.6 0.8 mAh/cm
2
Total Capacity: 0.7 0.8 Ah
Stack (12 layers) of bipolar electrodes
Ionic Liquid-based Lithium-ion Batteries
ELECTROLYTE ELECTRODES PROTOTYPE STACK OF ELECTRODES
Li-Ion cells (LFP-LTO) with Ionic Liquid-based Electrolytes
Very promising
cycling performance
LTO / 0.9PYR
14
FSI 0.1LiTFSI / LFP
Pouch Cell, glass fiber, 20C
CMC binder aqueous slurries Al collectors
Appetecchi G. B, et al.
J . POWER SOURCES 196, 6703-6709, 2011
Vacuum test
1- Two identical vacuum sealed cells differing only for the electrolyte
2- The cells are placed under the same vacuum level
ORGANIC ELECTROLYTE IONIC LIQUID
Operation under
vacuum
Aluminum in PYR
14
TFSI - LiTFSI electrolytes
0 40 80 120
0,00
0,05
0,10
0,15
0,20
0,25
0,30
j
/
m
A

c
m
-
2
t/min
PC-LiTFSI
80wt% PYR
14
TFSI +20wt% PC +LiTFSI
PYR
14
TFSI -LiTFSI
0 200 400 600
0,00
0,01
0,02
0,03
0,04
0,05
j
/
m
A

c
m
-
2
t/min
PC-LiTFSI
80wt% PYR
14
TFSI +20wt% PC +LiTFSI
PYR
14
TFSI -LiTFSI
(80%PYR
14
TFSI-20%PC)-LiTFSI PYR
14
TFSI-LiTFSI PC-LiTFSI
Chronopotentiometry at 4.6 V vs. Li/Li
Al corrosion suppressed with TFSI-based electrolytes
1
R.-S. Khnel,et al, J . Power Sources, in press (2012)
HighVoltageElectrodes:ILvs Carbonates@4.8V
Very high capacity after long-term cycling
High coulombic efficiency (pract. 100%)
Li / Electrolyte / Li[Li
0.2
Mn
0.56
Ni
0.16
Co
0.08
]O
2
Pouch Cell @ 40C and C/2
High-Energy (Next-Generation) Battery Technologies
>500 Wh/kg
Revolutionary
Technology-
Change
Pb-acid 3000 kg
Ni-MH 1200 kg
Super- Battery < 200kg
Li-ion Batteries
Year
Present 2017
170 Wh/kg
*
250 Wh/kg
*
Estimated
limit of
Lithium-Ion
Technology
" 4V"
Li-Ion
Oxide
Cathodes
Li-Element batteries
1
2
3
4
5
6
250 500 750 1000 1250 1500 1750
4000
3750
P
o
t
e
n
t
i
a
l

v
s
.

L
i
/
L
i
+
0
0
Capacity / Ah kg
-1
Li
metal
O
2
(Li
2
O)
F
2
S
O
2
(Li
2
O
2
)
Lithium-Element
Battery Cathodes
Theor. Energy: 3000-5000 Wh/kg
4 Li + O
2
2 Li
2
O E=2.91
V
2 Li + O
2
Li
2
O
2
E=3.10
V
Combustion Energy of Gasoline
Theor. Energy: 13500 Wh/kg
Practical Energy: 2700 - 3000 Wh/kg
C
8
H
18
+25/2 O
2
8 CO
2
+9 H
2
O
CO
2
CO
2
+H
2
O
Gasoline
Li
2
O
Li
2
O
2
Li
13500
3750
3000
11700
5200
3500
Anode
(Li/Li
x
Si)
Li
+
ion
conducting
electrolyte
-
Li
+
Li
Li
2
O/Li
2
O
2
Air
Li
+
V
I
Oxygen
harvesting
Lithium-electrolyte
interface
KEY ISSUES OPEN
Oxygen Redox
reaction
Target:
500Wh/Kg & 200W/kg at the
battery pack
Li-Air batteries: Splitting the Issues
O
2
Participant organisation name Country
Westfaelische Wilhelms-Universitaet Muenster (WWU) DE
Tel Aviv University (TAU) IL
Consejo Superior de Investigaciones Cientificas (CSIC) ES
Kiev National University of Technology and Design (KNUTD) UKR
University of Bologna (UNIBO) IT
University of Southampton (SOTON) UK
SAES Getters S.p.A. (SAES) IT
Chemetall DE
AVL List GmbH (AVL) AT
Volkswagen (VW) DE
European Research Services GmbH (ERS) DE
EU Project LABOHR
FP7-2010-GC-ELECTROCHEMICAL STORAGE
265971
Conventional electrolytes based on carbonates and ethers have been
ruled out because of insufficient stability for ORR
F F
O
O
O
O
S S
N
-
F
F
F
F
F
F
O
O
O
O
S S
N
-
F
F
F
F
F
F
F
F
F
F
F
F
O
O
O
O
S
S
N
-
F
F
F
F
F
F
F
F F
F
O
O
O
O
S S
N
-
CH
3
C H
3
N
+
CH
3
O
C H
3
N
+
4 anions vs. 2 cations
FSI
BETI
TFSI
IM14
PYR
14
+
PYR
12O1
+
Investigated ILs for Li-Air cells
0 50 100 150 200
-20
-15
-10
-5
0
5
10
15
20
Stripping on Ni
o
Plating on Ni
o
C
e
l
l

O
v
e
r
v
o
l
t
a
g
e
(
m
V
)
Cycle Number
0.25mAcm
-2
at 20
o
C
-20
-15
-10
-5
0
5
10
15
20
190
th
100
th
150
th
50
th
1
st
0.25mAcm
-2
at 20
o
C
C
e
l
l

O
v
e
r
v
o
l
t
a
g
e
(
m
V
)
Cycle
0 5 10 15 20 25
0
5
10
15
20
25
-
j
Z
'
'
(
O

c
m
2
)
Z'(Ocm
2
)
After 180 cycles
Li plating/stripping from IL-based electrolytes
Li / 0.1LiTFSI-0.9PYR
14
FSI/Ni (20C, 0.25 mAcm
-2
, sealed cell)
Very promising cycle performance
Li plating/stripping from IL-based electrolytes
Li / 0.1LiTFSI-0.9PYR
14
FSI/Ni (20C, various current rates,sealed
cell)
Limited rate performance
Li plating/stripping from IL-based electrolytes
Li / 0.1LiTFSI-0.9PYR
12O1
TFSI/Li (60C sealed cell)
Open challenge: 1 mAcm
-2
Effect of (dry) air on Lithium plating/stripping
Li
+
Li / IL / Ni
Li
+
Li / IL / Ni
e
-
e
-
10h plating at 0.1 mA cm
-2
Cycles of 1h stripping / 1h plating
0.1 mA cm
-2
, V
cut-off
= 0.5V
Pyr
12O1
FSI: LiTFSI 9:1 (open dry air)
Good cycling performance even in presence of air
PYR
14
is more stable than PYR
12O1
in dry air
Pyr
12O1
FSI: LiTFSI 9:1
20C
37 cycles
Eff = 86.4%
Pyr
14
FSI: LiTFSI 9:1
20C
59 cycles
91.5%
Lithium Metal Polymer Batteries (LMPBs)
10
-2
Scm
-1
10
-3
Scm
-1
10
-6
Scm
-1
10
-7
Scm
-1
Organic Liquid Electrolytes
Room T
conductivity
10
-4
Scm
-1
Polymer + LiX
10
-5
Scm
-1
- no liquid compounds
- high safety
- high energy density
- very good processability
but . poor RT conductivity
Incorporation of ILs has resulted in high ionic conductivity SPEs
Polymer + LiTFSI
large
anion X
-
IL
Polymer + LiX
+ Ionic Liquid*
J .-H. Shin, et al.. Electrochem. Comm. 2003, 5, 1016. Ionic liquids to the rescue? Overcoming the ionic conductivity limitations of polymer electrolytes.
PEO-LiX-IL electrolytes: SPEs
Poly(ethylene oxide)
PEO, n ~91.000
Molecular weight ~4 Mio.
Composition is given as:
Molar ratio of P(EO) : Li salt : IL
[ 20 : 2 : 4 ]
Li TFSI PYR
14
TFSI Benzophenone
Good adhesiveness
Excellent mechanical properties
PEO-LiX-IL electrolytes: conductivity and
stability
Laminated, vacuum
sealed Li/SPE/Ni cells
wide ESW
High ionic conductivity
Excellent mechanical, chemical
and electrochemical stabilities
high chemical stability
Laminated, vacuum
sealed Li/SPE/Li
cells
PEO : LiTFSI : PYR
14
TFSI = 20:2:4 (mol)
Lithium and
electrolyte layers Bipolar cathode
Cell stack
Vacuum Sealed Cell
Lithium metal electrode operation appears
feasible in IL-based electrolyte
Li/ IL-based electrolyte/ LFP
1Ah prototype
Li / P(EO)
10
LiTFSI-PYR
14
TFSI / LiFePO
4
Very large capacity increase due to IL incorporation > 100 mAhg
-1
at 20C
Theoretical capacity (170 mAhg
-1
) at 30C
Battery tests: PEO-IL-LiX electrolyte (RT tests)
PEO-LiX-IL electrolytes
How do ILs enhance Li
+
conduction?
TFSI
-
Li
+
PEO host
Li
+
Li
+
TFSI
-
PYR
+
PYR
+
TFSI
-
PEO-LiX electrolyte: Li
+
is strongly
coordinated by PEO host
PEO-LiX-IL electrolyte:
solid ternary system composed by a polymer
host (PEO) and two salts (LiTFSI and
PYR
14
TFSI)
very weak interactions between PYR
14
+
and
TFSI
-
[1]
no interaction between PYR
14
+
and PEO host
(Raman & NMR) [2,3]
strong interactions between Li
+
and TFSI
-
(in excess)
the strength of the Li--PEO
coordination lowered
the lithium mobility (Li
+
conduction)
is promoted
1
M. Castriota, T. Caruso, R. G. Agostino, E. Cazzanelli, W. A. Henderson, and S. Passerini, J. Phys. Chem. A 109 (2005) 92
2
I. Nicotera, C. Oliviero, W. A. Henderson, G. B. Appetecchi, and S. Passerini J. Phys. Chem. B 109 (2005) 22814.
M. J oost et al, Electrochim. Acta, in press 2012
PEO-LiX-IL electrolytes: Li interface (40C)
Impedance is localized at the Li/SPE interface
R1 R2
CPE1
CPE2
R3
W1 C1
R
1
= bulk electrolyte resistance
R
2
= Li/SPE interface 1
CPE
1
= Li/SPE interface 1
R
3
= Li/SPE interface 2
CPE
2
= Li/SPE interface 2
W
1
= Warburg impedance
C
1
= electrode limit capacitance
0 150
___ Raw Data
___ Fit
Z
-
j
Z

Li / P(EO)
20
(LiTFSI)
2
(PYR
14
TFSI)
n
/ Li
Transport properties by DC tests
How much current can be flown through the SPE?
Lithium
SPE
Galvanostatic and
Potentiostatic
experiments
Capacity of Li foil (Chemetall):
50 m * 1 cm = 5mm 10.32 mAh/cm
Transport properties by galvanostatic tests (30C)
IL containing electrolytes perform well at 30C
Dendrites due to
inhomogeneity of
ionic conduction
Li / P(EO)
20
(LiTFSI)
2
(PYR
14
TFSI)
n
/ Li
Transport properties by potentiostatic tests (30C)
Good agreement between galvanostatic and potentiostatic results
Li / P(EO)
20
(LiTFSI)
2
(PYR
14
TFSI)
4
/ Li
0.05 mAcm
-2
@ 0.2 V
Transport properties by DC tests
Complete stripping of 50 m of lithium (ca. 10 mAh cm
-2
)
Li / P(EO)
20
(LiTFSI)
2
(PYR
14
TFSI)
n
/ Li
bottom
lithium
SPE,
slightly
oxydised
Left over
edge of top
lithium
Area of
stripped
lithium
Lithium
SPE
Transport properties by DC tests
Opened cell after full lithium plating
Li / P(EO)
20
(LiTFSI)
2
(PYR
14
TFSI)
n
/ Li
Open cell
SPE
Plated lithium
Transport properties by DC tests
SEM of fresh lithium, plated lithium and SPE
Li / P(EO)
20
(LiTFSI)
2
(PYR
14
TFSI)
n
/ Li
fresh lithium plated lithium SPE on stripped lithium
Ionic Liquid mixtures with lithium salts as such and in
presence of polymers show very promising performance
as Li-ion conductors.
IL-based electrolytes:
easy to recycle (low volatility)
wide storage temperature range
low flammability components
high temperature operation capability (>60C)
IL-based electrolytes appear promising for safe, high
energy and moderate power applications (such as full EV
and stationary storage).
Conclusions
Acknowledgements
German and NRW funding agencies
The European Commission for the financial support of the projects:
ILLIBATT (Ionic Liquid based LIthiumBATTeries)
LABOHR (Lithium Air Batteries with split Oxygen Harvesting and Reduction processes)
GREEN LION (Advanced Manufacturing Processes for Low Cost GREENer Li-ION
Batteries)
All members of WWU-MEET and ENEA battery groups
Back up
Methods
relaxation measurements
1) spin-lattice-relaxation time T
1
:
inversion recovery
2) spin-spin-relaxation time T
2
:
CPMG-sequence
diffusion measurements:
pulsed gradient stimulated echo
sequence
d1

180y 90
x

erstes
Echo
180y
zweites
Echo
usw.
first
ECHO
second
ECHO
d1 t t t
t t
d1
180
x
90
x
t
90
x
t
T
A
o
o
g
g
markaspin
positionbythe
precessionphase
readthespin
positionafter
timeA
z
1
z
2
g:gradientstrength
o:gradientduration
A:diffusiontime
t:evolutiontime
z
1
andz
2
:spinpositionbeforeandafterthegradients
90
x
90
x
local motion macroscopic motion
N
+
C H
3
CH
3
Is the Li
+
--- TFSI
-
ion-pairing avoidable?
Pyr
+
14
Pyr
+
1(2O1)
Cation aggregation in ILs with polar side chains
for systems with Li salt AR does
not change
aggregation of cations w/ polar
group
cations do not aggregate when
a lithium salt is dissolved
pure IL IL with Li salt
N
+
C H
3
CH
3
R
2
dependent on chain length in pure systems
slow local motions influenced
R
1
independent on chain length in pure systems
fast local motions not influenced
AR changes with chain length
anisotropical arrangement
PYR
+
1A
Li
+
TFSI
-
interactions
Raman
Addition of oxygen into side
chain reduces the number of
TFSI anions in cluster.
Addition of oxygen into side
chain reduces the number of
TFSI anions in cluster.
P
y
r
1
4
T
F
S
I
P
y
r
1
5
T
F
S
I
free TFSI
-
Li
+
---
TFSI
-
P
y
r
1
(
2
O
1
)
T
F
S
I
P
y
r
1
(
2
O
2
)
T
F
S
I
Diffusion coefficient
diffusion of Li
+
slower than those of
Pyr
1A
+
and TFSI
-
coordination clusters hindered in
motion
difference of diffusion coefficients
larger for polar side chain than for
non-polar side chain
mobility of lithium ions not
enhanced by coordination of
pyrrolidinium cation
M. Kunze, et al., J PC C (2011)
N
+
C H
3
CH
3
Tailored Ionic Liquid for Lithium Batteries
Purity > 99.5%
H
2
O < 1ppm
T
d
:
175C
o
RT
: >3 mS/cm
o
15C
: 1 mS/cm
ESW: > 5.0 V
PYR
14
FSI
T
m
: -
18C
Paillard et al., J ES 156, A891(2009), Kunze et al. J PC A 114, 1776 (2010)
Pyr
+
14
Li
+
TFSI
-
interactions
NMR-chemical shift
NMR features of oxygen
neighbours are strongly affected as
a result of the Li --- IL Cation
interactions
Red:pureIL
Black:ILwith salt
ILLIBATT Project achievements
7
Page 7
Page 9
Demonstrated feasibility of Ionic Liquid-based batteries at the pre-
industrial scale
ILLIBATT has been selected together with other most successful
projects within the FP5 and FP6 calls
Materials for a sustainable chemistry
European Commission, Research Directorate-General
Directorate G-Industrial Technologies-Value-added Materials
ILLIBATT Cells:
Do not contain volatile components
Halides are present only in the easy-to-
recycle electrolyte
All binders are halide-free
Large capacities (140 mAhg
-1
) up to medium rates (C/5)
Moderate capacities (50-75 mAhg
-1
) even at high rates (2C-1C)
> 90% of initial capacity is delivered upon about 200 cycles
Battery tests: PEO-IL-LiX electrolyte (near RT tests)
Li / P(EO)
10
LiTFSI-PYR
14
TFSI / LiFePO
4
PEO-LiX-IL electrolytes: Li interface
Excellent lithium plating/stripping performance
Lowered interface resistance
PEO : LiTFSI : PYR
14
TFSI = 20:2:4 (mol)
Lithium
electrodes
SPE
Plated Li SPE Depleted Li