nanoparticles in lithium -ion batteries – opportunities ... · 17/32 electrochemistry laboratory...
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Electrochemistry Laboratory – Batteries
NanoparticlesNanoparticles in Lithiumin Lithium--Ion Batteries Ion Batteries ––
Opportunities and ChallengesOpportunities and Challenges
Timothy PateyTimothy Patey
R. R. BBüüchelchel, S.H. Ng, F. , S.H. Ng, F. KrumeichKrumeich, S.E. , S.E. PratsinisPratsinis, , P. P. NovNováákk
Paul Scherrer Paul Scherrer InstituteInstitute
Electrochemistry LaboratoryElectrochemistry Laboratory
Villigen, SwitzerlandVilligen, Switzerland
Electrochemistry Laboratory – Batteries2/32
OutlineOutline
• Electrochemical energy storage and the Li-ion batteries
• Nanoparticles for Li-ion Batteries
• Co-synthesis of LiMn2O4 and carbon black nanocomposites
• Outlook of research
Electrochemistry Laboratory – Batteries3/32
Electrochemical energy storage in the energy economyElectrochemical energy storage in the energy economy
1. Static load levelling of renewable energy
Shanghai, China
Electrochemistry Laboratory – Batteries4/32
Electrochemical energy storage in the energy economyElectrochemical energy storage in the energy economy
1. Static loading levelling of renewable energy
2. Transportation
Both Toyota and Mercedes will release HEVs with Li-ion batteries in 2009
Electrochemistry Laboratory – Batteries5/32
Specific Energy [Wh/kg]
Lithium-Ion
Pb/PbO2
ElectrochemicalCapacitors
1 10 100 1’0001
10
100
1’000
10’000
100’000
1’000’000
Sp
ecif
ic P
ow
er
[W/k
g]
RagoneRagone--plotplot
Electrochemistry Laboratory – Batteries6/32
ElectrochemistryElectrochemistry
� 4 V
LiCoO2,
LiNiO2,mixed
LiMn2O4
LiFePO4
Graphite
Hard Carbons
Electrochemistry Laboratory – Batteries7/32
WhyWhy notnot nanoscalenanoscale? ? �������� moremore surfacesurface areaarea = = increaseincrease in in sideside reactionsreactions
>
>
WhyWhy nanoscalenanoscale? ? �������� moremore surfacesurface areaarea = = increaseincrease in powerin power
Electrochemistry Laboratory – Batteries8/32
CoCo--synthesis of LiMnsynthesis of LiMn22OO44 and carbon blackand carbon black
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PreparationPreparation of of electrodeselectrodes
Composite
electrodeAssemble into cell
Li anode (-)
Electrolyte:
LiPF6 in EC/DMC
Separator
Composite
electrode (+)
Flame-made
powder
Carbon black
Binder
+
+
Mix contents in
polar solution[7:2:1]
1
1 - 10% polyvinylidenfluoride (PVDF) 1015 dissolved in n-methyl-2-pyrrolidon (NMP)
Electrochemistry Laboratory – Batteries10/32
Cyclic Cyclic voltammogramsvoltammograms –– reaction kineticsreaction kinetics
-600
-400
-200
0
200
400
600
3 3.2 3.4 3.6 3.8 4 4.2 4.4
Voltage, U (V)
Sp
ecif
ic C
urr
en
t, j
m (
mA
g-1
)
56 % flame-made CB
32 % flame-made CB
0 % flame-made CB
Charge
(Li+ extraction)
Discharge
(Li+ insertion)
LiMn2O4Li1-xMn2O4,
x � 0.7
Electrochemistry Laboratory – Batteries11/32
Discharge capacity per unit mass LiMnDischarge capacity per unit mass LiMn22OO44
0
20
40
60
80
100
120
0 10 20 30 40 50 60 70
Cycle Number
Dis
ch
arg
e C
ap
acit
y (
Ah
kg
-1)
56 % flame-made CB
32 % flame-made CB
0 % flame-made CB
0.5C1C 2C 5C 10C 20C 50C
Electrochemistry Laboratory – Batteries12/32
Discharge capacity per unit mass electrodeDischarge capacity per unit mass electrode
0
20
40
60
80
100
120
0 10 20 30 40 50 60 70
Cycle Number
Dis
ch
arg
e C
ap
acit
y (
Ah
kg
-1)
56 % flame-made CB
32 % flame-made CB
0 % flame-made CB
50C
0.5C1C 2C 5C 10C 20C
Electrochemistry Laboratory – Batteries13/32
Layout of a lithiumLayout of a lithium--ion battery ion battery –– consideration of consideration of
nanocompositenanocomposite (32wt.% carbon black) in a battery (32wt.% carbon black) in a battery
159 �m
20 �m 10 �m20 �m 20 �m
658 �m
LiMn2O4 Electrode / Al Electrolyte C6 Electrode / Cu
Electrochemistry Laboratory – Batteries14/32
Specific Energy [Wh/kg]
Lithium-Ion
Pb/PbO2
ElectrochemicalCapacitors
1 10 100 1’0001
10
100
1’000
10’000
100’000
1’000’000
Sp
ecif
ic P
ow
er
[W/k
g]
RagoneRagone--Plot Plot ––
LiMnLiMn22OO44 / CB / CB nanocompositesnanocomposites as hybrid materialas hybrid material
Electrochemistry Laboratory – Batteries15/32
ConclusionsConclusions
• Battery with LiMn2O4 / carbon black nanocompositescould have a specific energy one order of magnitude greater than supercapacitators, but…
• Coating of nanoparticles required to reduce capacity fading over the lifetime of the battery (>1000 cycles).
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Other activities Other activities –– past and presentpast and present
• Synthesis of LiV3O8 cathode material by FSP.
• Electrode optimization of TiO2 using surfactants.
• Optimization of LiMn2O4 nanoparticles by FSP.
Electrochemistry Laboratory – Batteries17/32
Other activities Other activities –– past and presentpast and present
• Synthesis of LiV3O8 cathode material by FSP.
• Electrode optimization of TiO2 using surfactants.
• Optimization of LiMn2O4 nanoparticles by FSP.
Other activities Other activities -- futurefuture
• Advanced electrochemical characterization at the Tokyo Institute of Technology, Prof. M. Nakayama
• Electrochemical impedance spectroscopy
• Electrochemical calorimetric measurements
Electrochemistry Laboratory – Batteries18/32
AcknowledgmentsAcknowledgments
THANK YOU FOR YOUR ATTENTION!