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AmiensAmiens
US DOE EFRC Summit and Forum
Washington DCRenaissance Penn Quarter Hotel
May 25th-27th, 2011
Jean Marie TARASCON
Key challenges and new trends inbattery research
Outline
Personal view of the future of batteries
Present ongoing research activities to tackle them
Conclusions ?
Flash recall on why energy storage …EU and French research structuring initiatives …
Rapid assessement of today’s state of the art in Li-ion batterySpot/highlight present limitations and upcoming issues (recycling)
Mention/discuss a few chemistries beyond Li-ion
A few comments beyond science
PHOTO-SYNTHESIS
BIOMASS
-CHOH-
CO 2
O2
O2
SUN
Energy
ENERGY
H2O
-CHOH-
COMBUSTION
7 kWh/kg
4.3 kWh/kg
h
6 CO2 + 6 H2O
C8H12O8 + 6 O2
H2O
CO2
O2
O2
PHOTO-SYNTHESIS
BIOMASS
-CHOH-
CO 2
O2
O2
SUN
Energy
ENERGY
H2O
-CHOH-
COMBUSTION
7 kWh/kg
4.3 kWh/kg
h
6 CO2 + 6 H2O
C8H12O8 + 6 O2
6 CO2 + 6 H2O
C8H12O8 + 6 O2
H2O
CO2
O2
O2
FOSSIL FUELS13 kWh/kg
Millionsof years
95 MBa/day
3.7 milliards1.35 tep/hab
20001970 2030
5
10
17.7
Consommation Mondiale Annuelle
(109 tep)8.2 milliards2.2 tep/hab
6 milliards1.7 tep/hab
6 892 760 01213:00 aujourd’hui
3.7 milliards1.35 tep/hab
20001970 2030
5
10
17.7
Consommation Mondiale Annuelle
(109 tep)8.2 milliards2.2 tep/hab
6 milliards1.7 tep/hab
6 892 760 01213:00 aujourd’hui
20001970 2030
5
10
17.7
Consommation Mondiale Annuelle
(109 tep)8.2 milliards2.2 tep/hab
6 milliards1.7 tep/hab
6 892 760 01213:00 aujourd’hui
3.7 Billions1.35 tep/hab
World AnnualConsumption
108 tep
6 Billions1.7 tep/hab
8.2 Billions2.2 tep/hab
3.7 milliards1.35 tep/hab
20001970 2030
5
10
17.7
Consommation Mondiale Annuelle
(109 tep)8.2 milliards2.2 tep/hab
6 milliards1.7 tep/hab
6 892 760 01213:00 aujourd’hui
3.7 milliards1.35 tep/hab
20001970 2030
5
10
17.7
Consommation Mondiale Annuelle
(109 tep)8.2 milliards2.2 tep/hab
6 milliards1.7 tep/hab
6 892 760 01213:00 aujourd’hui
20001970 2030
5
10
17.7
Consommation Mondiale Annuelle
(109 tep)8.2 milliards2.2 tep/hab
6 milliards1.7 tep/hab
6 892 760 01213:00 aujourd’hui
3.7 Billions1.35 tep/hab
World AnnualConsumption
108 tep
6 Billions1.7 tep/hab
8.2 Billions2.2 tep/hab
14 TW
28 TW
Renewable EnergiesRenewable EnergiesRenewable Energies
WHY ENERGY STORAGE ?
Bill
ions
de
bar
ils /
an
Années Découvertes à venir
Consommation
Réserves découvertes
Bill
ions
de
bar
ils /
an
Années Découvertes à venir
Consommation
Réserves découvertes
gap
Consumption
Discovery
Projected discoveriesyears
Energy storage:Another challenge of the 21st century
Chemical Electric
To improve-create new energy storage technologies
Wind Solar Oceans
To better handle therenewable energy resources
of our planet
MWh kWhElectric
To favour thedevelopment of electric vehicles
Wind Solar Oceans
To better handle therenewable energy resources
of our planet
MWh kWhElectric
To favour thedevelopment of electric vehicles
To develop better electrochemical energy storage devices
Batteries
Restructuring of the scientific and technological landscape via the creation of new federative tools
MaterialsMaterials for for EnergyEnergy Storage & ConversionStorage & Conversion
ALISTOREEducation Programme
http://www.u-picardie.fr/mundus_MESC
MaterialsMaterials for for EnergyEnergy Storage & ConversionStorage & Conversion
ALISTOREEducation Programme
http://www.u-picardie.fr/mundus_MESC
MaterialsMaterials for for EnergyEnergy Storage & ConversionStorage & Conversion
ALISTOREEducation Programme
http://www.u-picardie.fr/mundus_MESChttp://www.u-picardie.fr/mundus_MESCE
I
R
E
I
R
ELITE (75 k€/an) SILVER (25 k€/an)
11
4
EDFSaftArkemaUmicoreSolvionicHoneywellSolvayESATOTALBASFSasol
CEARenaultVolkswagenRobert Bosch
Aeronautic &Space users
PV’s usersCar makers MaterialMakers
BatteryMakers
Cell-phonemakers
15 members15 members
Business of industrial club membersBusiness of industrial club members
ALISTOREALISTORE--ERI Industrial Club compositionERI Industrial Club composition
ELITE (75 k€/an) SILVER (25 k€/an)
11
4
EDFSaftArkemaUmicoreSolvionicHoneywellSolvayESATOTALBASFSasol
CEARenaultVolkswagenRobert Bosch
ELITE (75 k€/an) SILVER (25 k€/an)
11
4
ELITE (75 k€/an) SILVER (25 k€/an)
11
4
EDFSaftArkemaUmicoreSolvionicHoneywellSolvayESATOTALBASFSasol
CEARenaultVolkswagenRobert Bosch
Aeronautic &Space users
PV’s usersCar makers MaterialMakers
BatteryMakers
Cell-phonemakers
15 members15 members
Business of industrial club membersBusiness of industrial club members
ALISTOREALISTORE--ERI Industrial Club compositionERI Industrial Club composition
18 European Research Labs_
European Initiative: ALISTORE-ERILaunched in 2004 (FP6) with the incorporation of industries in 2008
The Research/Innovation/EducationTriangle
Partenaires Industriels
Management/Direction
Research CenterCRA CRTI
● University + CNRS labs
● Pre-transfert unitsResearchers + engineers
Bordeaux, Nantes, Montpellier, Toulouse, Orleans, Pau, AmiensMarseille,Paris-tech, …….
Technology Research and integration Center● Nationnal Labs (EPICs )CEA, INERIS, IFP, …
- Industrialisation platforms- Safety platform- BMS platform- Testing platform
Industrial Club(14 Members)
CI
R hR hMaillons nécessaires pour l’intégration rapide en un produit fini.
Intégrer et fédérer tous les acteursTo ensure a continuum from research to development via
prototyping and then a quick transfer to our industriesMaillons nécessaires pour l’intégration rapide en un produit fini.
Intégrer et fédérer tous les acteursTo ensure a continuum from research to development via
prototyping and then a quick transfer to our industries
Research and Technology National Network on Electrochemical Energy Storage (RS2E)
(Created July 2010)
Primary cells
Rechargeable(Batteries)
Li / S
CuO
CuS
CuOCu4O(PO4)2
Solidcathodes
I2 SO2Liquid
cathodes
SOCl2
CFx
MnO2Ag2CrO4
Ag2CrO4
CrOx
Li/I2Li/SOCl2
Li/SO2Li/MnO2 Li/FeS2
Li/Cfx
Bi2Pb2O5
Bi2O3
FeS2
Ag2V4O11
Composés d’insertionTiS2
Electrolyte polymèrePEO
Chlorides, sulfides, fluorides…
Plastifiants
V6O13
NbSe3
NiPS3
MoS2
MnO2LiCoO2LiNiO2
Li/PEO/VOx
Li ionLiCx
LiCx/LiCoO2
LiMn2O4LiNCALiNMC
LiFePO4
19491949
19601960
19701970
19801980
19901990
20062006
Jan Hajek
?
Genealogic tree for Li-based batteries
From . Broussely (adapted)
Li-airLi-air
Li-airLi-air
Li-airLi-air
V
Non-aqueous electrolyte
Cathode Anode
Li+
Li+
3.0 V
+
LiMnLiMn22OO444.2- 5 V
LiCoOLiCoO22--NMCNMC4.2- 4.6 V
LiFeSOLiFeSO44FF3.6 - 4 V
LiLi22FeSiOFeSiO44
LiLiLiFePOLiFePO443.45 V
-
ac
TiO2(B)TiO2(B)1.8 V
LiLi44TiTi55OO12121.5 V
LiLixxSiSiyy0.4 VLiLixxCC66
0.2 V
The Li-ion technology:A versatile technology in terms of potential
The Li-ion technology:a versatile technology in terms of power
Battery
Supercapacitors
ENERGY DENSITY (Wh/kg) AUTONOMY
SP
EC
IFIC
PO
WE
R (W
/kg)
S
PE
ED
# ## ## #
The Li-ion technology: a large potential market
………… WhWh kWh kWh MWhMWh …………………… WhWh kWh kWh MWhMWh …………
2 MW Li-ion storage
EV’s pack
Different energy domainsDifferent materialsDifferent safety and cost aspects
186505-10Wh 30-100kWh
210Wh/kg
625Wh/l
Is it sufficient for EVs applications ?
Today’s state of the art performancefor the Li-ion technology
ForesightForesight
HigherHigher RateRate
HigherHigher EnergyEnergy
LowerLower CostCost
HigherHigher SafetySafety
ForesightForesight
HigherHigher RateRate
HigherHigher EnergyEnergy
LowerLower CostCost
HigherHigher SafetySafety
Challenges Facing batteries for EVsapplications
LowerLower CostCostLowerLower CostCostSustainabilitySustainability
Materials/processes having the minimum environmental footprint and lowest possible life cycle cost
500 € /kWh
130Wh/kg
/ 2 x2x2
*Source:Nedo (2009)
500 € /kWh
130Wh/kg
/ 2 x2Energyx2
*Source:Nedo (2009)
Cost
Durability
The Li-ion batteries: Sustainable aspects
Energy-demanding step(e.g. high CO2 released
10 Billionbatteries peryear in 2010: compulsory
recycling
Oresextraction
Battery +
_
Ashes with
Oresextraction
Electrode elaboration via HT processes
Recycling
Purification
+
_
metal co
ntents
Battery
ass
embly
Thermal treatment
The way we are making batteries today:
Energy-demanding step
Energy needed ≈ 287 kWhFabrication of a battery of 1 kWh
CO2 rejected: ≈ 110 kgNeed to make more sustainable and “greener” Li-ion batteries
Life Cycle Analysis of Large-size Li-ion secondary batteries, K. Ishihara et al. (2009)
Moleculesextraction
CO2 +
_Biomasse
Assembling
Recycling
2 +
_
Elaboration of electrochemically active materials via the
“green” chemistry concepts
Biomass
Ideal Situation
Routes followed• Elaboration of inorganic materials via eco-efficient processes• Use of organic materials as renewable Li electrodes• Other chemistries : Na-ion
Tomorrow’s needs and challenges:Develop sustainable Li-ion batteries
Ceramic process Solvothermal
process Hydrothermalprocess Ionothermal
process Bio-mineralizationprocess
Bulk NanoLower temperatures Economy of atoms
700°C 120°C 180°C
q
NN NN
TFSI -
NN NN
TFSI -
q
NN NN
TFSI -
NN NN
TFSI -
200°C 60°CSolution reactionsSolid state
reactions
Towards energy saving processesfor materials preparation
Ionothermal approach to the synthesis of inorganic compounds
N. Recham, M. Armand and J-M. Tarascon Patent Filed N°: 2110141 (2008)
Ionic liquidsMolten salts at ambient temperature
Solvent recycling : classic organic route washing CH2Cl2-centrifugation
Time= 5hTime= 5hTime= 5h
Flask
Synthesis at ambient pressure up toT= 300-350°C
°CC°CC
Autoclave
NN NN
TFSI -
NN NN
TFSI -
NN NN
TFSI -
NN NN
TFSI -No vapour tension
Thermal stability > 300°C
Non flammable
Good solvent for numerous salts and polymers
cations-anions combinations (estimated at 15000, 1000 realized)
1 5 2 0 2 5 3 0 3 5 4 01 5 2 0 2 5 3 0 3 5 4 02, CoK
?
? ? ????
?
(200)
(101)
(210) (011)(111)
(211)
(301)
1h
3h
5h
7h
24h
Inte
nsity
LiFePO4 FeC2O4.2H2O Li4P2O7 Fe3O4 LiPO3
1h
24h
5h
2 Co K
24 hrs
7 hrs
5 hrs
3 hrs
1 hrs
mm1
100-200nm
mm1
100-200nm
N. Recham, L. Dupont, D. Larcher, M. Armand, and J-M. Tarascon Chemistry of Materials 21(6), (2009), 1096-1107.
LiH2PO4 + FeC2O4.2H2O
LiFePO4 + 3 H2O + CO2
EMI-TFSI
220-250°C
Ionothermal synthesis of LiFePO4: The case example
Ionic liquids as reacting media: Beneficial Aspects
Synthesis of numerous known phases at T =200°C (ceramic routes T 700°C)
Na2Fe(Mn)PO4F
LiFe(Mn)PO4F
LiFePO4
Li2FeSiO4
Changing and adjusting the size and morphology of the powders
NN
+N
F3
CO
2S
SO
2C
F3
-
NN
+C
N
NF
3C
O2
SS
O2
CF
3-
100-200nm100 à 200nm100-200nm100 à 200nm
New electrochemical active materials Via ionothermal synthesis
New family of Fluorosulfates AMSO4F, A= Li, Na; M =Fe, Ni, Co
N. Recham, J-M. Tarascon et al.: Nat Mater. 2010, 9(1), 68-75.
2
2.5
3
3.5
4
4.5
0 0.2 0.4 0.6 0.8 1po
tent
ial v
s. L
i+ /Li
x in LixFeSO
4F
60
80
10 0
12 0
14 0
16 0
0 10 20 30 40 50
Cap
acity
(mA
h/g)
N um be r o f c yc le
3.6 V
140 mAh/g
Unstable: Decompose for T> 320°CSoluble in water
285°C, 24hMSO4. H2O + LiF LiMSO4F
EMI-TFSI
285°C, 24hMSO4. H2O + LiF LiMSO4F
EMI-TFSI
Serious contender to LiFePO4
P. Barpanda, J-M. Tarascon et al.: Angewendte . 2011, 9(1), 68-75.
LiFeSO4F LiZnSO4F LiMnSO4F
Tavorite TripliteSillimaniteP-1 Pnma C2/c
Fluorosulfates LiMSO4F: a true challenge for theorists
LiFeSO4F LiZnSO4F LiMnSO4F
Tavorite TripliteSillimaniteP-1 Pnma C2/c
Why different structures depending on M ?DFT + U calculations give little thermodynamic differences; less than kBT…??.
Make theory more predictive: To reach the point where new compounds together with their properties can be predicted
Key challenge …
Unstable: Decomposes for T> 320°C
Towards the eco-efficient elaborationof electrode materials: a few tendencies
Return to life chemistry
● To develop bio-assisted, bio-inspired or bio-mimetic synthesis approaches to
elaborate known or new inorganic materials
Fe2O3
Can we make electrode materials at toom temperature ?
From bacteria to electrode materials
bio-mineralization approachBacillus pasteurii « Urease » kinetically controls urea hydrolysis
Collaboration: F. Guyot (Université de Paris VI)
LiFePO4 synthesis
T = 60°CH2N NH2
OLiH2PO4 + + FeSO4.7H2O LiFePO4 + (NH4)2SO4
50 nm
020
10-1000
11-1
12-1
010dd
8 hours
50 nm
Fabrication of Genetically Engineered Lithium Ion Batteries
Electrodes from genetically modified viruses+
-
aa--FePOFePO44/CNT/CNT
CoCo33OO44/Au/Au
ModifiedM13 virusModified
M13 virus
+
-
aa--FePOFePO44/CNT/CNT
CoCo33OO44/Au/Au
ModifiedM13 virusModified
M13 virusaa--FePOFePO44/CNT/CNT
CoCo33OO44/Au/Au
ModifiedM13 virusModified
M13 virusModified
M13 virusModified
M13 virusModified
M13 virusViruses are Used as
building blocks,templates
Growth of nano-composite
conducting electrodes
Bio-mineralization or virus engineering offers a new approach to design sustainable electrodes
J-M. Tarascon; Nature nanotechnology, 4-341-342(2009)Nam, K.T. et al. Science. 312, 885-888 (2009).
Inorganicelectrodes
Possibility of using
organic electrodesMineral
Further inspiration from life chemistry
Looking for electrochemically active organic electrodes
M2C6O6 (with M = Li, Na, K, Rb and Cs)Get inspiration from the old chemistry on oxocarbons
OO
OO
LiO
LiO
OLiO
LiO
O
O
LiO
LiO
O
O
O
LiO
LiOOxocarbones2
Croconate
Squarate
Deltate
Rhodizonate
2. West, R. & Powell, D. L. New aromatic anions. III. Molecular orbital calculations on oxyganated anions. J. Am. Chem. Soc., 85, 2577-2579 (1963).
1. N. Ravet, C. Michot, M. Armand, Mater. Res. Soc. Symp. Proc., 496, 263-173 (1998).
0
0.5
1
1.5
2
2.5
3
3.5
4
2 2.5 3 3.5 4 4.5 5 5.5 6
Pot
entia
l(V
vs.
Li/L
i+ )
x in Li2+xC6O6
4 injected e- / unit formula
0
0.5
1
1.5
2
2.5
3
3.5
4
2 2.5 3 3.5 4 4.5 5 5.5 6
Pot
entia
l(V
vs.
Li/L
i+ )
x in Li2+xC6O6
4 injected e- / unit formula
myo-inositol Lithium Rhodizonate
O
O
O
O
L iO
L iO
. 2 H 2 O
O H
O H
O H
H O
H O
H O
1 ) H N O 3
2 ) O 2 , , Acet. de Li
How to make Li2C6O6 from natural resources ?
Preisler, P. W. & Berger, J. Am. Chem. Soc., 64, 67-69 (1942).
8 % of the dry weight of corn-steeping liquor
6
OH
OH
OH
HO
HO
HO
OPO3H2
OPO3H2
OPO3H2
H2O3PO
H2O3PO
H2O3PO
myo-Inositol
Chemical/enzymaticdiphosphorylation
Phytic-acidFrom
biomass
to
a
ctive electro
de
(25% yield)
The field of organic chemistry:a fertile domain for sustainable electrodes
Flexibility of the redox potential according to the nature and environment of the electro-active centre
0
2
100 300200 400 500
1
3 Carbonyle
mAh/g
Pot
entie
l (V
vs.
Li)
O
O
OLi
OLiLiO
LiOO
O
OLi
OLiLiO
LiO
Ester
O
O
OLi
LiO
O
O
OLi
LiO
CarboxyleO
-O O
O- Li+
Li+
O
-O
O
-O-O O
O-
O
O-O- Li+
Li+
+
_
O
O
O
O
LiO
LiO O
O
O
O
LiO
LiO
Chem sus chem 2008
JACS 2009
JACS 2010
Nat. Mat. 2009
Chem. Com. 2011
Jr. Mat.Chem 2011
reducing
oxidizinga
Elaboration of the1st organic and bio-compatible Li-ion battery …
Good thermal stabilityGood cycling behaviourPoor performance
x in
00,5
11,5
22,5
33,5
4
2 2,5 3 3,5
Pote
ntia
l/V v
s. L
i 6C 6O6
xC
6O
6
CycledcellCycledcellLi2C6O6/Li6C6O6 Ion cell
More ecological systemsNew concept
Main remaining issue ??
Find highly oxidizing Li-based organic electrodes to be used
as Li reservoir
Li2C6O6 2Li+ + 2e- + C6O6 Li2C6O6 2Li+ + 2e- + C6O6 Li2C6O6 2Li+ + 2e- + C0/CO2
February 3, 2009Peak Lithium: Will Supply Fears Drive Alternative Batteries?
February 3, 2009Peak Lithium: Will Supply Fears Drive Alternative Batteries?
Tuesday, February 3, 2009Bolivia: The Saudi Arabia of lithium?
Tuesday, February 3, 2009Bolivia: The Saudi Arabia of lithium?
Key numbers:160 000 tons Li2CO3 annual production20-25% for battery sector (>32 000 tons)Roughly 0.5 kg of Li2CO3 per 1kWh battery
Simple estimation if:10 % of the 60 million cars are pure EVs(25kWh): 75 000 tons : half of today’s total production
Li Resources (13 M of T)
●Mineral: ●Salars: ● See water:0.2 ppm
Issues in Lithium resourcesSustainability
BEST Spring, 37-41(2009) US. Geological survey (2007) Under the microscope, MIR (2008)
A few alternatives
To promote recycling
Simple considerations toproduce 1 Ton of Lithium
250 T 750 T 28 T
● To develop Li-recovery processes Hydro-metallurgy
● Higher availability of precursors
Post-lithium chemistry:the sodium alternative ?
Na-3.04 -2.71Li
3860 1166
Electrode potential (V) Electrode capacity mAh/g)
Na-3.04 -2.71Li
3860 1166
Electrode potential (V) Electrode capacity mAh/g)
Na-3.04 -2.71Li
3860 1166
Electrode potential (V) Electrode capacity mAh/g)
Li1s22s1
Lithium
6.9413
0.534180.50.98 Na
2s23s1Sodium
23.94111
0.97980.9 Li1s22s1
Lithium
6.9413
0.534180.50.98 Na
2s23s1Sodium
23.94111
0.97980.9
Na in Earth: 103 ppmNa in Sea : 105 ppm
● Lower performance than Li-Ion
Potentially cheaper than Lithium chemistry
Reincarnation chemistry of materials will become an
essential part of future battery business
From Li-ion to Na-ion batteries
Still a material problem
Capacité (mAh/g)
0.5
2.0
1.0
4.5
1.5
2.5
4.0
3.0
3.5
10050 150 200 250
Pot
entie
l (V
vs.
Na+
/Na)
Pos
itive
sN
égat
ives
NaVPO4F
Na0.44MnO2
Na0.6 CoO2
Na0.6 Mo2O4 Nax(MoO2)2 P2O7
NaxC
Na2FePO4F
NaFeSO4F
V2O5
MoO3NaTi2(PO4)3
Na3V2(PO4)3
MoSe2
Na2C8O4H4a
Key Challenge: To find new negative electrode materials ?
1
1 , 5
2
2 , 5
3
3 , 5
4
4 , 5
1 1 , 2 1 , 4 1 , 6 1 , 8 2
Pote
ntia
l (V
) vs
Na+ /N
a
x i n N ax
F e P O4
F
3.1 V
B.L. Ellis , L.F. Nazar et al. .,,Nature Materials 6, 749 – 753, (2007)
1 , 2
1 , 4
1 , 6
1 , 8
2
2 , 2
2 , 4
2 , 6
0 , 5 0 , 6 0 , 7 0 , 8 0 , 9 1
Pot
entia
l (V
vs.
Na+ /N
a)
x i n N ax
V O2
( P )
1.6 V
P. Rozier, J.M. Tarascon et al. (submitted)
Sustainability
y
Poten
tial
Neg
ativ
eP
ositi
ve
Energy aspects
Capacity
Pote
ntia
l (V
vs.
Li+ /L
i)
Energy
Energy= Capacity x Potential
Increased energy density
ab
c
1.75 Li
Li2MnSiO4 60°C
Increased capacity (2e- per 3d-metal?)
Increased potential V (5 V ?)
Vol
tage
x in Li2-xCoPO4F
6V
5V
4V
LiCaCoF6???
Co, Ni)PO4n1.5Ni0.5]O4LiMnPO4
LiMn2O4Ni, Me)O2
6V
5V
4V
LiCaCoF6???
Co, Ni)PO4n1.5Ni0.5]O4LiMnPO4
LiMn2O4Ni, Me)O2
6V
5V
4V
LiCaCoF6???
Co, Ni)PO4n1.5Ni0.5]O4LiMnPO4
LiMn2O4Ni, Me)O2
6V
5V
4V
LiCaCoF6???
Co, Ni)PO4n1.5Ni0.5]O4LiMnPO4
LiMn2O4Ni, Me)O2
ENERGY Short and mid-term developments
Thermal vs. Electrical vehicles
1 liter of gaz2300Wh/Kg
1kg of Li-ion 150Wh/Kg
A factor 15 gap
How to close the gap between Octane vs. Li-ion?
ENERGYENERGY
Which chemistries are around the corner ???
(Revisiting Li-S and Metal- air systems and more so the Li-air system)
Li-S Li-O2
2Li+ + 2e- + S Li2S (E°= 2,27 V )Energy density = 3802 Wh/kg
2Li ++ 2e- + O2 Li2O2 (E°= 3,14 V) Energy density = 5259 Wh/kg
natural, abundant,
cheap
feedstock
≈380 Wh/kg
Factor of 10
≈180 Wh/kg
0,5Li+ + 0,5e- + Li0,5CoO2 LiCoO2 Energy density = 550 Wh/kg
x 3≈ 500 Wh/kg
Factor of 10
What are these “attractive” technologies?What can we expect ?
The Li-oxygen battery
C_MnO2
C_MnO2
Progresses have been achieved, but major problems remain ..
Nano MnO21000mAh/g
Capacity in mAhg-1 (carbon)
Vol
tage
(vol
ts v
s. L
i)
Collaboration avec P. Bruce: University of St-Andrews, Scottland
0.7 V
Shao-Horn – JACS_132_12170_2010:
Discharge Reaction :Discharge Reaction :2 Li2 Li++ + 2 e+ 2 e-- + O+ O22 LiLi22OO22
O2 + e- O2·-
O2 + e- O2
·-
Li-air _ the numerous challenges
● To reduce the voltage gap ● To master electrode porosity
CathodeAnode● Inherits problems of Li
dendrites
Electrolyte● Master the O2
.- reactivity● O2 solubility, diffusivity
Commercial rechargeable Li-air cells have still a long way to go either at the research or applied levels: Be careful …
Pote
ntia
l
Capacity
Anodes + Cathode +
Electrolyte problems
High fading + poor rate capability
Worldwide Estimated Global installedCapacity energy storage:
Source : www.storagealliance.org
TOTAL: 125,520MW
98%
Batteries:
98%
Pumpedhydro 451 MW
1.5% of the consumption
1980 1990 2000 2010
VehicleVehicleLiLi--ion (Niion (Ni--Co, Co, MnMn, Ni, Ni--MnMn ・・)・・)
Billions of $Billions of $
S tationaryS tationaryNaSNaS , Zn, Zn--Br, ZnBr, Zn--C lC l, R F Ni, R F Ni--MH, LiMH, Li--ion ion
billions of $billions of $S tationaryS tationaryNaSNaS , Zn, Zn--Br, ZnBr, Zn--C lC l, R F Ni, R F Ni--MH, LiMH, Li--ion ion
billions of $billions of $
Stationary market will expand
● Great opportunities for innovative Redox-Flow chemistries
● NaS is stellar
● Li-ion is entering
Mass storage energy (MW) :Could Li-ion play a role ?
Sony
Sony
1990 2005
Conversion
Cathodes (nano)
20151995
Ener
gy d
ensi
ty
Sony
250 Wh/kg, 800Wh/l
A123
2007
??????
2004
LiM
nOmiEV / C0 / Lion
2 MW Li-ion battery
Cathodes
organiques
Futur Futur
Li-air
Futur
x 2 ou 3
Na-ion
chemistry
Li-S
FuturSus
taina
ble de
velop
ment
e
Outlook for Li-ion batteries over the next 20-30 years
Conclusions: Beyond scientific challenges ..
Research funding worldwide (EVs + Batteries)
Is it really a problem of money ?More a problem of managing/structuring for efficient integrationbetween science and technology
Solving energy issues is a worldwide problemFind means/tools to foster worldwide cross-sharing information on pre-competitive topics between each national scientific program
Countries/continentscreate their own programs,
set-up new federative infrastructures
Energy Frontiers Research Centers (US) European Network of Excellence
(ALISTORE-ERI) French Hub (RS2E) in 2010 reuniting
(researchers, engineers, users)
US:US:9,17b€
EU:EU: 1,2b€
ASIA:ASIA:>3,3b€
Thank you for your attention
ALISTORE_ERI
LiLi
LRCSRS2E
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