Chaire annuelle Anne acadmique 2010-2011

Chaire Dveloppement durable

Environnement, nergie et Socit
Pr of . Jean- Mar i e Tar ascon
Amiens
History and development of
Batteries technology
February 2nd 2011
Portable devices
1-100Wh
Growing addicted to batteries
Wind
Solar
Tides
To better handle
renewable energy resources
of our planet
MWh
To favour the
development of electric
transportation
Electric
kWh
SourceTakeshita2010
A profitable and fully expanding market
Years
P
r
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s
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t

m
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k
e
t

i
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b
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s

o
f

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o
s
Today
Batteries and electric vehicle
Electric vehicle
La jamais contente
(1899)
109 km/h
Autonomy: 80 km
Edison Model 1920
Lead batteries
Batteries and cellular phone
The cellular phone in 1920
Hello? We are coming by car and well be there
in 15 mns
Radiotelephone
conversation
The battery of Baghdad: The first battery?
(-200 BC)
AE = 0,8 V
Electrolyte :
(weak acid:
Fruit juice)
Historically and scientifically speaking, the assumption
of the battery remains to this day hardly plausible
Cu
Fe
From Galvanis frog to the Voltaic battery
A frogs leg will respond
when in contact
with two different
metals
Electricity is produced
by the thigh
Fe
Cu
GALVANI
1781
1781
WRONG !
VOLTA
1797
VOLTA
1797
Fe
Cu
1797
Cell
column
Stacking of
Zn-Cu metal disks
each one separated by
cloth soaked in an electrolyte
1800
Electricity is produced
by the thigh
A frogs leg will respond
when in contact
with two different
metals
Voltaic batteries
Other technologies being
developed
Li-air, Li-S systems
Rechargeable batteries
Pb-acid technology
Ni technologies (Ni-Cd, Ni-MH,..)
2000
1800
1900
Na technologies (HT-BT)
History and development of batteries:
Outlines
Daniell, Leclanch
The electrochemistry behind
Li-ion technologies,..)
2050
A few of these reactions imply a straight forward exchange of electrons
Oxydo-reducing (redox) reactions between an oxidizing agent and a reducing one
Chemistry electronic Interactions between atoms or structures of atoms
Chemical reaction Reorganization of these electronic interactions
(oxydant) Cu
2+
+ 2e- Cu (rducteur)
(rducteur) Zn 2e- + Zn
2+
(oxydant)
Cu
2+
+ Zn Cu + Zn
2+
(oxydant) Cu
2+
+ 2e- Cu (rducteur)
(rducteur) Zn 2e- + Zn
2+
(oxydant)
(oxydant) Cu
2+
+ 2e- Cu (rducteur)
(rducteur) Zn 2e- + Zn
2+
(oxydant)
Cu
2+
+ Zn Cu + Zn
2+
Cu
2+
+ Zn Cu + Zn
2+
Experiment 1 : a Cu blade in a Zn
2+
solution
Cu + Zn
2+
Zn + Cu
2+
Experiment 2 : a Zn blade in a Cu
2+
solution
Zn + Cu
2+
Cu + Zn
2+
A few notions of electrochemistry
1,23 Volts
Electrolyse
H
2
O H
2
+ O
2
Redox potential (Volts) Semi-reactions
1,10 V
Cu
2+
Zn(s) Zn
2+
Cu(s)
Classification of electrochemical potentials
Scale of potentials
How to study these reactions?
How to control these reactions?
How to recover this energy?
The movement of the ions must
be separated from that of the
electrons
The creation of a battery
Strong
oxidants
Weak
oxidants
Weak reducing
agents
Strong reducing
agents
global reaction : Cu
2+
+ Zn Cu + Zn
2+
Zn
2+
Cu
2+
AV
SO
4
2-
SO
4
2-
Saline bridge (ionic junction)
Cu
Couple Cu
2+
/ Cu
Zn
Couple Zn
2+
/ Zn
1,10 V
Cu
2+
+ 2e- Cu
Reduction
Cathode
Zn Zn
2+
+ 2e-
Oxidation
Anode
SO
4
2-
What are the main characteristics
of a battery?
Daniell (1836), Becquerel (1829):
Batteries with separated compartments
POTENTIAL (AE, Volts,..)
Walther Nernst (1890)
Nobel Chemistry 1920
Cu
2+
Zn
Cu
Zn
2+
Cu
2+
Zn
Cu
Zn
2+
Cu
2+
Zn
Cu
Zn
2+
A
E = 1,1 V
A
E = 0,0 V
End of reaction
| |
| |

.
|

\
|
+ =
Reducing
agents
Oxidants
Log
nF
RT
E Eelectrode 10
- Nature of the redox couples
- State of advancement of the reaction
POTENTIAL (AE, Volts) CAPACITY (Q, Coulomb,
Faraday, Ah)
- Nature of the redox couples
- Quantity of material
Specific energy
(Wh/litre, Wh/kg)
Specific power
(W/litre, W/kg)
How to increase the energy density
of a battery
Number of exchanged electric charges (Coulombs)
POTENTIAL
CAPACITY
ENERGIE
ENERGIE
ENERGY
Number of exchanged electric charges (Coulombs)
CELLS
Alkaline, Lithium,
Mercury, Silver
MnO
2
Zn
Zn
2+
MnO
2
/MnOOH couple
Reduction/Cathode
2 solids
Zn
2+
/ Zn oxide
Oxidation/Anode
KOH
(aq.)
AE = 1,5 V
MnO
2
+ H
+
+ e- MnOOH Zn Zn
2+
+ 2e-
AV
H
+
Alkaline cell (1950) derived from the
salt cell (Leclanch, 1868)
Number of exchanged electric charges
(Coulombs)
D
i
f
f
e
r
e
n
c
e

i
n

p
o
t
e
n
t
i
a
l

(
V
o
l
t
s
)

From cells to batteries
300
200
100
0
E
n
e
r
g
i
e

v
o
l
u
m
i
q
u
e


(
W
h
/
l
)
0 50 100 150
Energie massique (Wh/Kg)
400
Gain de poids
plomb
-Acide
200 250
Ni-Cd
Ni-
MH
Li-ion
Li-Mtal.
(scurit)
G
a
i
n

d
e

t
a
i
l
l
e

2V
1.2V 1.3V
3.6V
3.5V
300
200
100
0
E
n
e
r
g
i
e

v
o
l
u
m
i
q
u
e


(
W
h
/
l
)
0 50 100 150
Energie massique (Wh/Kg)
400
Gain de poids
plomb
-Acide
200 250
Ni-Cd
Ni-
MH
Li-ion
Li-Mtal.
(scurit)
G
a
i
n

d
e

t
a
i
l
l
e

2V
1.2V 1.3V
3.6V
3.5V
Plus lgre
P
l
u
s

p
e
t
i
t
e
Ni-
Zn
Anode : oxidation. Cathode : reduction.
During disharge : cathode = + and anode =
Batteries
Pb/acid, Ni/Cd, Ni/MH,
Ni/H
2 ,
or ion Li
Reversible reactions
Battery =
cells
Mass energy
Which battery to travel 40 to 50 kms?
Necessary energy: 300 to 360 Wh (36 V, 8 to 10 Ah)
The size of the batteries is linked to the volume of energy density , Wh/L
From 13-15 kg to 3-4 kg according to the type
China: 150 and 200 millions of EAV (nearly 20 million per year!).
Electrically-assisted?
Comparison in terms of energy and power
Batteries
Super-
capacitors
Low energy and specific power (25-35 Wh/Kg; 60-120Wh/l)
Reduced cyclability and calendar life, weak in temperature
Its cost (100 /kWh)
Gaston Plant and Lead:
First battery (1859)
AE = 2,0 V
PbO
2
(s) + 4H
+
+ SO
4
2-
+ 2e-
PbSO
4
(s) + 2H
2
O
Pb(s) + SO
4
2-
PbSO
4
+ 2e
-
Reactions in the solid state:
Breaking of chemical bonds at both electrodes
Usable batteries for thermal vehicles
Industrial batteries (network support, heavy traction)
PbSO
4
4 H
+
Pb PbO
2
SO
4
2-
PbSO
4
H
2
SO
4
/ H
2
O
v
++
_
I/A
SO
4
2-
H
2
O
-
The Ni-Cd batteries and its derivatives
Ni-Fe, Ni-Zn, Ni-H
2
and Ni-MH
Insertion positive electrode Ni(OH)
2
<=> NiOOH
I
n
t
e
r
m
e
t
a
l
l
i
c
s
Nickel - Metal Hydride cells(1.32 V)
M
(s)
+ xH
2
O + xe
-
MH
x(s)
+ xOH
-
- A. Percheron, J.H. Van Vucht (1975)
- Commercialized in 1988 (Toshiba)
M = La, Ni, , V, Ti, Co, rare earths
Cd
Nickel-Cadmium cells(1.3 V)
Cd(OH)
2
(s)
+ 2e
-
Cd
(s)
+ 2OH
-
- Waldmar Jungner (Sweden, 1900),
- Commercialized en 1947
45-65 Wh/kg
Nickel-Zinc cells (1.73V)
Zn(OH)
2
(s) + 2e
-
Zn
(s)
+ 2 OH-
- Commercialized: SCPS
Z
n
70 Wh/kg
H
2
Nickel-Hydrogen batteries
2H
2
O + 2e
-
H
2
+ 2OH
-
80 Wh/kg
600
600
+ HOH + e
-
Ni(OH)
2
NiOOH
+ OH
-
+ HOH + e
-
+ OH
-
Structure hte
maintenue
Pas de rupture
de liaisons
Electrolyte aqueux
KOH
600
600
+ HOH + e
-
Ni(OH)
2
NiOOH
+ OH
-
+ HOH + e
-
+ OH
-
The host
structure
Is maintained
No bonds
splittings
Aqueous electrolyte
KOH
Volume energy (310Wh/L)
Cyclability
Strong power
Cost of materials
Mass energy (80Wh/kg)
1975: the Nickel-Metal hydride battery:
Two insertion reactions
(Hydroxyde lamellaire)
v
+
_
Ni
OH
OH
Ni
OH
OH
Ni
OH
OH
Ni
OH
OH
Ni
OH
OH
Ni
OH
OH
Ni
OH
OH
Ni
OH
OH
Ni
OH
OH
Ni
OH
OH
Ni
OH
OH
Ni
OH
OH
H
+
H
+
OH
-
H
2
O
H
+
H
+
OH
-
H
2
O
H
+
H
+
H
+
H
+
OH
-
H
2
O
OH
-
H
2
O
+
_
Aqueous electrolyte (KOH)
Ni(OH)
2
(s) + OH
-
NiOOH(s) + H
2
O + e
-
Ni
OH
OH
Ni
OH
OH
Ni
OH
OH
Ni
OH
OH
Ni
OH
OH
Ni
OH
OH
Ni
OH
O
Ni
OH
O
Ni
OH
O
Ni
OH
O
Ni
OH
O
Ni
OH
O
M + xH
2
O + xe
-
MH
x
+ xOH
-
H
H
H
HH
HH
H
H
H
M
MH
x
NiOOH
Ni(OH)
2
AE = 1,3 V
1997, Toyota Prius
Performances
80Wh/kg
2001350W/kg
600cycles
"LaNi
5
H
6
"
+ 6H
+
+ 6e
-
"LaNi
5
"
From 1960: growing interest
in the use of lithium
Li
1s
2
2s
1
Lithium
6.941
3
0.534
180.5
0.98
H
1s
1
Hydrogen
1.0079
1
0.089
14.5
2.2
Weak ionic ray
fast diffusion Power
Works in aqueous medium
Limits thermodynamics to 1.2 V
0 4 2 10 6 8 12
pH
E (Volts vs. H
+
/H
2
)
0
-1.2
1.6
1.2
0.8
0.4
-0.4
-0.8
O
2
H
2
O
H
2
0 4 2 10 6 8 12
pH
E (Volts vs. H
+
/H
2
)
0
-1.2
1.6
1.2
0.8
0.4
-0.4
-0.8
O
2
H
2
O
H
2
pH
E (Volts vs. H
+
/H
2
)
0
-1.2
1.6
1.2
0.8
0.4
-0.4
-0.8
O
2
H
2
O
H
2
The lightest of metals (6.9 g), d= 0,53g/cm
3
Most electropositive element => AE de 3 4 V
Better mass
Energy
density
Strong chemical reaction (water)
Non aqueous electrolytes: Organic
Li
1s
2
2s
1
Lithium
6.941
3
0.534
180.5
0.98
Li
1s
2
2s
1
Lithium
6.941
3
0.534
180.5
0.98
Primary
(batteries)
Rechargeable
(cells)
Li / S
CuO
CuS
CuO
Cu4O(PO4)2
Solid
cathodes
I2
SO2
Liquid
cathodes
SOCl2
CFx
MnO2
Ag2CrO4
Ag2CrO4
CrOx
Li/I2
Li/SOCl2
Li/SO2
Li/MnO2
Li/FeS2
Li/Cfx
Bi2Pb2O5
Bi2O3
FeS2
Ag2V4O11
Insertion compounds
TiS2
Polymer electrolyte
PEO
Chlorides, sulfides, fluorides
Plasticizers
V6O13
NbSe3
NiPS3
MoS2
MnO2
LiCoO2
LiNiO2
Li/PEO/VOx
Li ion
LiCx
LiCx/LiCoO2
LiMn2O4
LiNCA
LiNMC
LiFePO4
1949
1949
1960
1960
1970
1970
1980
1980
1990
1990
2006
2006
Jan Hajek
?
Family tree of Lithium ion batteries
De M. Broussely (SAFT)
Li metal rechargeable batteries:
A story with a bad end!
First Li intercalation
compounds
X
T
X
X
T
X
X
T
X
Li
X
T
X
Li
+
e
-
P
Te Oc
X
T
X
X
T
X
X
T
X
Li
X
T
X
Li
+
e
-
X
T
X
X
T
X
X
T
X
X
T
X
X
T
X
Li
X
T
X
Li
+
e
-
P
Te Oc
(1970-1973)
TiS
2
, MoS
2
,
1980-1989
Commercialization
Of Li/MoS
2
Batteries
by Moli Energy
Incidents on
Cellular phones
End of metal Li
rechargeable batteries
and
liquid electrolytes
Li dendrites
at recharge
Short-circuit
through the separator
Explosion
V
Liquid organic
electrolyte
Insertion compound
Metal Li
Li
+
Li
+
Metal Li (1975 ->
<-
I
e
-
->
Solutions put forward to solve
the security aspect
Rechargeable
Metal Li
Li-Polymer
Technology
Li-ion
Technology
1980s
M. Armand
D.W. Murphy, B. Scrosati
et al.
Li
+
PEO
- limitation of the dendrites
formation
- absence of organic solvents
- low ionic conductivity
- good functioning at 80C
T=80C
e
-
e
-
Positive
electrode
lithium
+
-
Polymer
electrolyte
Polymer electrolyte battery: Li-ion
Elimination of dendrites
PEO Electrolyte
Assembling
Commercialization 2011???
Bollor
BLue Car
Elimination of dendrites
Rechargeable Li-ion batteries
Concept (1980) Commercialization : Sony (1990)
B
a
t
t
e
r
y

v
o
l
t
a
g
e
Capacity (mAh/g)
Voltage ( 3.6V)
Nbr. Of lithiums per molar mass
LiC
6
Li
+
+ C
6
+ e
-
Specific
capacity:
M
Molar mass (kg)
26,8 x Ax
=
Nbr of e
-
or Li
+
Ah/kg
VV
Li
1-x
CoO
2
+ x Li
+
+ x e
-
LiCoO
2
lectrolyteliquide
Non-aqueux
Cathode
Anode
Li
+
+ -
Li
+
Non aqueous
electrolyte liquid
-
Cathode
Anode
Li
+
+ -
Li
+
(LiCoO
2
)
(Graphite)
Search for new materials
J-M. Tarascon and M. Armand. Nature, 2001, 414 (359-367)
LiNiO
2

Sn
P
o
t
e
n
t
i
a
l
v
s
L
i
/
L
i
+
(
V
)

Capacity (Ah/kg)
0 200 400 600 800 1000 1200 3800 4000
N
e
g
a
t
i
v
e
m
a
t
P
o
s
i
t
i
v
e
m
a
t
Li metal
Graphite
Other carbons Si-C
d = 2.3
Intermetallics
d = 4- 8
3D metal oxides
d= 7.5
Nitrides
d = 2.1
0
3
4
5
2
1
Sn-C
Phosphides (d ~ 8)
5V
LiCoO
2

LiMn
2
O
4

MnO
2

Vanadium oxides
(V
2
O
5
, LiV
3
O
8
)
(Li
1-x
VOPO
4
, Li
x
FePO
4
)
LiMnPO
4

LiCoPO
4

Li
4
Ti
5
O
12
Si
Doped LiMn
2
O
4

V
Li-ion
V
Li-metal
LiNiO
2

Sn
v
s
L
i
/
L
i
+
(
V
)

(Ah/kg)
0 200 400 600 800 1000 1200 3800 4000 0 200 400 600 800 1000 1200 3800 4000
N
e
g
a
t
i
v
e
m
a
t
e
r
i
a
l
s
P
o
s
i
t
i
v
e
m
a
t
e
r
i
a
l
s
Li metal
Graphite
Other carbons Si-C
d = 2.3
Intermetallics
d = 4- 8
3D metal oxides
d= 7.5
Nitrides
d = 2.1
0
3
4
5
2
1
0
3
4
5
2
1
Sn-C
Phosphides (d ~ 8)
5V
LiCoO
2

LiMn
2
O
4

MnO
2

(V
2
O
5
, LiV
3
O
8
)
Polyanionic compounds
(Li
1-x
VOPO
4
, Li
x
FePO
4
)
LiMnPO
4

LiCoPO
4

Li
4
Ti
5
O
12
Si
Doped LiMn
2
O
4

V
Li-ion
V
Li-metal
V
Liquid organic
electrolyte
Cathode
Anode
Li
+
Li
+
LiMn LiMn
2 2
O O
4 4
4.2- 5 V
LiCoO LiCoO
2 2
4.2 V
LiFeSO LiFeSO
4 4
F F3.6 V
Li Li
2 2
FeSiO FeSiO
4 4
3.0 V
a
c
TiO2(B) TiO2(B)
1.8 V
Li Li
4 4
Ti Ti
5 5
O O
12 12
1.5 V
Li Li
x x
Si Si
y y
0.4 V
Li Li
x x
C C
6 6
0.2 V
Li Li
LiFePO LiFePO
4 4
3.45 V
+ -
Li-ion technology:
A versatile technology
- good ionic conductivity
- functioning at ambient temperature
- Energy loss linked to the carbon anode
Li
+
+
Li
+
e
-
e
-
cathode Anode
(carbone)
+
-
Liquid electrolyte
in an inert polymer
separator
Li-ion plastic
(1994 - Tarascon et al.)
PVDF-HFP electrolyte
---
Assembling
Commercialization 2007
The Li-ion plastic technology:
Developed in 1994
Present performances of the
Li-ion technology
200 Wh/kg
550 Wh/l
MWh Li-ion
batteries
18650
5-10Wh
Batteries
for EVs
30-100kWh
A market dominated by Asia
Liion/NiMH /NiCd Batteries
distribution(2008) source:Avicenne
Volumedistributionof
Liionbatteries(2010)
source:Takeshita
Japan
53%
Others
13%
China
13%
Korea
20%
Europe
1%
Others
7%
Japan
41%
Korea
36%
China
16%
La recherche, November 2009 issue La recherche, November 2009 issue
Tesla roadster
Li-ion batteries in HEVs and EVs:
When is the large-scale application?
Widely advertised
Many cars manufacturers on the starting-blocks
Frequent statementsbut constantly postponed
What are the remaining stakes?
GM Volt
miEV / C0 / Lion
Bollor Bluecar
Numerous international and national
initiatives
Better
Place Leaf La Fluence
x2 x2
S
ustainable d
evelop
m
ent
x 0.1 x 0.1
A
d
v
a
n
c
e
d
e
le
c
t
r
o
ly
t
e
s
M
o
r
e

E
n
e
r
g
y
C
h
e
a
p
e
r
v
v
Li-ion technology: Safety factor
Internal short-circuits
Manufacturing incidents
A few incidents: Flamethrower batteries
August 2006: Sony calls back 6.5 million batteries
Loss of electrolyte
Users mistakes
Zero
risk
W
h
W
h
K
W
h
K
W
h
5 V
2 - 3 V
2V LiFePO
4
/
LiBOB/
Li
4
Ti
5
O
12
Redox
Shuttles
Electrolyte
additives
Shut-down
additives
SEI
modifiers
Shut-down
separators
Ionic
liquids
Coatings
Materials
chemistry
Improved safety
through chemistry
Battery management
system
Pressure liming
valve
PTC switch
Battery monitoring
system
Thermal
management
Improved safety
via cell
design and
electronics
*Solid state
Li-ion battery
LiCoO
2
LiFePO
4
Safety
Cost
Approaches to increase safety:
There is no Zero risk
+ 12.5 O
2
8 CO
2
+ 9 H
2
O
500 km
6 L/100 km < 30%
~ 100 kWh
Thermal vs. Electric vehicle:
How to fill the gap Octane vs. Li-ion
500 Kms autonomy
2020
500 kg
> 200 Wh/kg
Electrochemical
cells
Super-battery
<200 kg
> 500 Wh/kg
N
e
w

e
l
e
c
t
r
o
c
h
e
m
i
c
a
l
s
y
s
t
e
m
s
Which
Technologies
???
Today
140 Wh/kg
700 kg
(2010) 250 kg - 160 km
Wh/kg
Li-ion
Li-S
Performances of the metal-air systems
towards Li-ion and Li-S
Li- S ( lit hium- sulphur) and Li- O
2
( lit hium- air) bat t eries can pot ent ially increase t he
st orage capacit ies of t he present Li- ion bat t eries
L
i
+
1 /
4
O
2
L
i
+
1 /
4
O
2
L
i
+
1 /
2
O
2
Z
n
2
+
/
2
O
2
A
l
+
3
/
4
O
2
M
g
2
+
/
2
O
2
F
e
3
+
/
2
O
2
C
a
2
+
/
2
O
2
In non aqueous
medium
In aqueous
medium
0
1000
2000
3000
4000
5000
6000
Aqueous
Metal-air
Non aqueous
Metal-air
Lithium-sulphur Lithium-oxygen
2Li
+
+ 2e
-
+ S Li
2
S (E= 2,27 V )
Specific energy= 3802 Wh/kg
Natural, abundant
and cheap
feedstock
380 Wh/kg
Factor 10
Comparison between Li-air and Li-S
technologies
180 Wh/kg
0,5Li
+
+ 0,5e
-
+ Li
0,5
CoO
2
LiCoO
2
Specific energy = 550 Wh/kg
x 3
500 Wh/kg
Factor 10
2Li
+
+ 2e
-
+ O
2
Li
2
O
2
(E= 3,14 V)
Specific energy = 5259 Wh/kg
Li-ion
Comparison between Li-air and Li-S
technologies
Li-air
vs.
2Li + + 2e - + O
2
Li
2
O
2

Electrochemical
cell
Feedstock
System
Initial state
Electrochemical
Reaction
Capacity
Sustainable
development
Embarked in the positive
Closed
discharged
Limited by the quantity of Li
Extracted for the cathode material
No
LiCoO
2
0,5Li + + 0,5e - + Li
0,5
CoO
2
Absorbed from the environment
Opened
charged
Limited by the amount of formed
Li
2
O
2
Yes

Reaction:
Reaction:
2 Li
2 Li
+ +
+ 2 e
+ 2 e
- -
+ O
+ O
2 2
Li
Li
2 2
O
O
2 2
O
2
+ e
-
O
2
-
Li
+
+ O
2
-
LiO
2
2 LiO
2
Li
2
O
2
+ O
2
0 200 400 600 800 1000
2.0
2.5
3.0
3.5
4.0
4.5
P
o
t
e
n
t
i
a
l

v
s

L
i
+
/
L
i
0

(
V
)

Capacity of O
2
electrode (mAh/g)
Li
Li
+ +
Li Li
2 2
O O
2 2
O
O
2 2 Li anode Li anode Porous cathode Porous cathode
Positive = porous composite
Discharge
Discharge
Non aqueous electrolyte Non aqueous electrolyte
Structure of the Air electrode
To improve the kinetics of the reaction: Role of the catalyst
O
2
O
2
O
2
Li
+
O
2
O
2
Li
+
Non aqueous electrolyte
e
-
O
2
Li
+
e
-
e
-
O
2
catalyst
carbon
Triple interface
porosity
Reaction product
e
-
Li
2
O
2
O
2
Li
+
The Air electrode
Can we set up a a method to quickly select catalysts?
48 h
Super P
-Fe
2
O
3
-MnO
2
NiO
70 mA/g
carbone
CuO
-MnO
2
Choice of catalyst
0 1000 2000 3000
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
T
e
n
s
i
o
n

(
V
)
Capacity / mAh/g
carbone
Li
2
O
2 ( s)
2 Li + O
2
H
2
O
2 ( aq)
H
2
O + O
2

Triple Interface: solid-gas-liquid

Quick reaction
Slow reaction
cat cat
Quick determination of the catalytic activity of a material
towards the decomposition of a peroxide
V. Giordani, S. A. Freunberger, P. G. Bruce, J-M. Tarascon, D. Larcher, Electrochem. Solid-State Lett. 13 A180 (2010)
Fast screening of catalysts
For the Li-air electrode: Role of the catalyst
Li
2
O
2 ( s)
2 Li + O
2
H
2
O
2 ( aq)
H
2
O + O
2

cat cat
Catalyst
Carbon SP
Ligand
Li
2
O
2
t
H
2
O
2
E
V. Giordani, S. A. Freunberger, P. G. Bruce, J-M. Tarascon, D. Larcher, ESSL. 13 A180 (2010)
Study of the reaction kinetics:
Role of the catalyst
0,7 V
Capacity (mAh/g
carbone
)
0.7 V
Role of a-MnO
2
catalyst on the polarization
of the Li-air electrode
??
Collaboration avec P. Bruce (St-Andrews)
-8 -6 -4 -2 0
3,00
3,25
3,50
3,75
4,00
4,25
|-MnO
2
o-MnO
2
-MnO
2
Co
3
O
4
CuO
o-Fe
2
O
3
NiO
O
x
i
d
a
t
i
o
n

p
o
t
e
n
t
i
a
l

(
V
)
Ln k
25C
(s
-1
.g
-1
)
E
0
= 3,14 V
500
0
(Wh/kg)
1000
5 6
L
i
-
a
i
r
Li-ion
Li-air vs. Li-ion :
facteur 5 en densit dnergie
500
0
(Wh/kg)
1000
5 6
L
i
-
a
i
r
Li-ion
Li-air vs. Li-ion :
factor 5 in energy density
35
Achilles heel of these systems:
The electrolyte
PC (LiPF
6
0,1 M)
i
c
i
a
i
a
/i
c
<<1
0.1 V/s
Cyclic Voltamperogrammes
O
2
CO
2
Unstable electrolyte
Follow-up of the charge of a
discharged electrode in the
presence of PC-LiPF6
Using Mass Spectrometry
M
+
= Li
+
O
2
.-
nucleophilic attackOpening of the PC cycle Carbonates formation
To master O
2
.-
superoxide ion = enzymatic approach
Collaboration avec P. Bruce (St-Andrews)
What about Lithium?
Abondance:
01/06/2009
Bolivie: sur un baril de lithium
01/06/2009
Bolivie: sur un baril de lithium
vendredi 24 avril 2009
L'Amrique du Sud se veut l'Arabie Saoudite du futur !
vendredi 24 avril 2009
L'Amrique du Sud se veut l'Arabie Saoudite du futur !
February 3, 2009
Peak Lithium: Will Supply Fears Drive Alternative Batteries?
February 3, 2009
Peak Lithium: Will Supply Fears Drive Alternative Batteries?
Tuesday, February 3, 2009
Bolivia: The Saudi Arabia of lithium?
Tuesday, February 3, 2009
Bolivia: The Saudi Arabia of lithium?
20/08/2009
Le lithium, un mtal que le monde va s'arracher
20/08/2009
Le lithium, un mtal que le monde va s'arracher
sea water (0.2 ppm)
Resources: locations
2 main sources:
saline deposits
Minerals
13 Millions tons
Recycling?
Other resources
Bolivie
Chile
Argentine
B
r
a
z
i
l
Bolivia
Chile
Argentina
B
r
a
z
i
l
13 millions tons
Jules Vernes legacy
- Yes Sir. Sodium on its own can be consumed and the sea is a great
provider. Besides, I shall tell you that sodium batteries must be
considered as the most energetic
- Sodium ?
Li
1s
2
2s
1
Lithium
6.941
3
0.534
180.5
0.98
Na
2s
2
3s
1
Sodium
23.941
11
0.97
98
0.9
Cost
Na
2
CO
3
: 0.10 /kg
Li
2
CO
3
: 3.5 /kg
Resources
Terre: 10
3
ppm
Mer : 10
5
ppm
Performances
Na
-3.04 -2.71
Li
3860 1166
Electrode potential (V)
Electrode capacity mAh/g)
Performances < lithium, but meet sustainable development
"20 000 leagues under the sea (1869)"
Capacity (mAh/g)
From Li-ion to Na-ion batteries
A problem of materials: Synthesis
0.5
2.0
1.0
4.5
1.5
2.5
4.0
3.0
3.5
100 50 150 200 250
P
o
t
e
n
t
i
a
l

(
V

v
s
.

N
a
+
/
N
a
)
P
o
s
i
t
i
v
e
N
e
g
a
t
i
v
e
NaVPO
4
F
Na
0.44
MnO
2
Na
0.6
CoO
2
Na
0.6
Mo
2
O
4
Na
x
(MoO
2
)
2
P
2
O
7
Na
x
C
Na
2
FePO
4
F
NaFeSO
4
F
V
2
O
5
MoO
3
NaTi
2
(PO
4
)
3
Na
3
V
2
(PO
4
)
3
MoSe
2
Na
2
C
8
O
4
H
4
P
o
t
e
n
t
i
a
l
(
V

v
s
.

L
i
+
/
L
i

)
(c)
1
1.5
2
2.5
3
3.5
4
4.5
5
1 1.2 1.4 1.6 1.8 2
1
1.5
2
2.5
3
3.5
4
4.5
5
1 1.2 1.4 1.6 1.8 2
200 nm
28.5 nm
4
6
.
5
n
m
200 nm
28.5 nm
4
6
.
5
n
m
200 nm
28.5 nm
4
6
.
5
n
m
200 nm
28.5 nm
4
6
.
5
n
m
60
80
100
120
140
0 2 4 6 8 10
C
a
p
a
c
i
t
y
(
m
A
h
/
g
)
Number of cycles
60
80
100
120
140
0 2 4 6 8 10
C
a
p
a
c
i
t
y
(
m
A
h
/
g
)
Number of cycles
x in Na
2-x
FePO
4
F
N. Recham, J.N. Chottard, M. Armand, J.M. Tarascon, Electrochemical Solid State Letters (in press).
FeF
2
+ Na
3
PO
4
Na
2
FePO
4
F + NaF FeF
2
+ Na
3
PO
4
Na
2
FePO
4
F + NaF
48h
270C
N N
+ N F
3
CO
2
S SO
2
CF
3
-
From Li-ion to Na-ion batteries
Na insertion materials
(
0
2
0
)
(
0
0
2
)
(
0
2
2
) (
1
2
1
)
(
0
2
3
)
(

1
2
2
)
(
0
4
2
)
(
2
0
0
)
(
1
3
3
)
(
1
4
2
)
,

(
1
0
4
)
(
2
3
3
)
(

0
0
6
)
2
u
(), Cu K
o
(
0
2
0
)
(
0
0
2
)
(
0
2
2
) (
1
2
1
)
(
0
2
3
)
(

1
2
2
)
(
0
4
2
)
(
2
0
0
)
(
1
3
3
)
(
1
4
2
)
,

(
1
0
4
)
(
2
3
3
)
(

0
0
6
)
2
u
(), Cu K
o
Na
2
FePO
4
F
(a)
Na-S technology: a high temperature
system
2Na(l) 2Na
+
+ 2e
-
xS(I) + 2e
-
+ 2Na
+
Na
2
Sx(I) + e
-
The Na/S battery: Reactions
-2.7 V
-0.6 V
-2.1 V
Alumina |
300C
(Na
2
O-11Al
2
O
3
)
Performances(Na/S)
90110Wh/kg
400Wh/l
600cycles
Temp:300C
Lowcostmaterials
2 Na + xS Na
2
S
x
2 Na + xS Na
2
S
x
High temperature Na-S battery
The most coveted for network applications
World leader : NGK
4.2 MW and 8 MWsystems installed
at Hitachi and Tokyo
58 MWh energy
34 MW 2 MW
Smoothing out photovoltaic or wind energies ?
Alessandro Volta
(Cu/Zn)
Li-ion
Sony
(commercialization)
1859 Pb batteries
1899 Ni-Cd
1973 Metal-Li
1975 Ni-MH
1978 Li-ion concept
1979 Li-metal Polymer
Li-ion plastic
Telcordia
1801
1990
2000
Conclusions
1900 1950
2050
2000
0
100
200
x 3
x

2
Loi de Moore: capacit x 2 tous les 18 mois
?
Li-air
1900 1950
2050
2000
0
100
200
x 3
x

2
Loi de Moore: capacit x 2 tous les 18 mois
?
Li-air
+
_
Na
+
e
-
Na
+
3.0 V
2
Na
x
MO
y
+
_
Na
+
e
-
Na
+
3.0 V
2
Na
x
MO
y
Li-Air
Li-S
Na-Ion
Na-S
Zebra
H.T.
2050
Li Li- -ion ion
1990
2010 2000
LiCoO
2
/C
LiFePO
4
/C
LiCoO
2
/Co
2
Sn
LiCo(Mn,Ni)O
2
/C
LiMn
2
O
4
/C
Slow but substantial progress
Li-ion technology
(liquid or plastic)
Today
C
h
a
n
g
e
Radio-telephone
conversation