advanced batteries for automotive applications
TRANSCRIPT
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ADVANCED BATTERIES
FOR AUTOMOTIVE
APPLICATIONS
Donald R. Sadoway
Department of Materials Science & Engineering
Massachusetts Institute of TechnologyCambridge, Massachusetts
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GCEP Advanced Transportation Workshop October 11, 2005Sadoway
motivation
Imagine driving this:
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GCEP Advanced Transportation Workshop October 11, 2005Sadoway
motivation (continued)
without the need for this:
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GCEP Advanced Transportation Workshop October 11, 2005Sadoway
relevant enabling technology
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GCEP Advanced Transportation Workshop October 11, 2005Sadoway
The message
The road to autonomy is paved
with advanced materials.
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GCEP Advanced Transportation Workshop October 11, 2005Sadoway
specific energies of battery chemistries
(Wh/kg) (MJ/kg)
lead acid 35 0.13NiCd 45 0.16NaS 80 0.28NiMH 90 0.32Li ion 150150 0.540.54
gasoline 12,00012,000 4343
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GCEP Advanced Transportation Workshop October 11, 2005Sadoway
battery performance metrics
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GCEP Advanced Transportation Workshop October 11, 2005Sadoway
battery performance metrics
RagonePlot
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GCEP Advanced Transportation Workshop October 11, 2005Sadoway
Sadoway’s Rule
1 Wh/kg storage capacity
1 mile driving range
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GCEP Advanced Transportation Workshop October 11, 2005Sadoway
USABC long-term performance goals
operating temp. -40 to 85ºC
specific energy 200 Wh/kg @ C/3
energy density 300 Wh/L @ C/3specific power 400 W/kg
power density 600 W/Lcycle life 1000 cycles @ 80% DOD
service life 10 yearsultimate price ~ $100/kWh for 40 kWh packs
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Strong Opinions
Li SPB is the only technology capable of exceeding 200 Wh/kg
Li SPB is unique for its mechanical flexibility
new designs
Li SPB is the only technology capable of meeting safety specs
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The Periodic Table of the Elements
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GCEP Advanced Transportation Workshop October 11, 2005Sadoway
some relevant electrochemistry
Look at the inner workings of a lithium battery:
at the anode (-)
Li Li+ + e-
at the cathode (+)
Li+ + e- + LiXCoO2 Li1+XCoO2
Li+ + e- + Co4+ Li+ + Co3+
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technical obstacles
anodesafetycycle lifecapacity
e- e-
currentcollector
(Cu)
Li metal
LiXC
SnOX / Sn Li+
loadLiMOx carbon polymer
currentcollector
(Al)
electrolyteelectrical conductivityelectrochemical stability
cathodecapacity power cycle life
_ +
polymer
Li Li+ + e-
Li+ + e- + LiXCoO2 Li1+XCoO2
Li+ + e- + Co4+ Li+ + Co3+
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the polymer electrolyte dilemma
electrical properties of a liquid
mechanical properties of a solid
molten/plasticized polymers
crystallized/crosslinked polymers
liquid flow
low conductivity
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GCEP Advanced Transportation Workshop October 11, 2005Sadoway
block copolymer electrolytes
both components liquid low Tg
components mutually immiscible
Li+ solubility in (PEO)8 brushes
liquid-liquid immiscibility + covalent bonding
spatially constrained phase separation (nanoscale)
mechanical stability
secondary block (dimensional stability)
PEO-based block (ion-conduction)
add Li+ as LiCF3SO3
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PLUS:facile processingengineered nanostructures
block copolymer electrolytes
T > TODT, disordered
liquid-like
Li+Li+
Li+
solid-like
Li+
Li+
Li+
Li+
T < TODT, ordered
10 - 100 nm
secondary block (dimensional stability)
PEO-based block (ion-conduction)
locally a liquid globally a solid
add Li+ as LiCF3SO3
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1st-generation BCEs
C
H
C
3CH
H C
O
O
3CH)( 8
( )x
2CH
C
H
C
3CH
H
CH
C
O
O
3CH)n
( )y
( 2O
POEM PLMA, PnBMA, or PMMA
CH2
poly (oxyethylene methacrylate) poly (alkyl methacrylate)
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1st-generation BCEs
C
H
C
3CH
H C
O
O
3CH)( 8
( )x
2CH
C
H
C
3CH
H
CH
C
O
O
3CH)n
( )y
( 2O
POEM PLMA, PnBMA, or PMMA
CH2
poly (oxyethylene methacrylate) poly (alkyl methacrylate)
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GCEP Advanced Transportation Workshop October 11, 2005Sadoway
1st-generation BCEs
C
H
C
3CH
H C
O
O
3CH)( 8
( )x
2CH
C
H
C
3CH
H
CH
C
O
O
3CH)n
( )y
( 2O
POEM PLMA, PnBMA, or PMMA
Tg ~ -60°C-35°C, (n = 11)
Tg ~ 40°C, (n = 3)100°C, (n = 0)
dope with lithium triflate, [EO]:LiCF3SO3 = 20:1.
CH2
poly (oxyethylene methacrylate) poly (alkyl methacrylate)
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synthesis of polymer electrolyte
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charge/discharge testing
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0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
0 2000 4000 6000 8000 10000
volta
ge (V
)
rate = C/2 room temperature
100% solid-state!
charge/discharge testing
capacity (mAh/g)
Li ⏐ Li+ ⏐ VOx
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Scalable Synthesis Routes: graft copolymer electrolytes (GCEs)
Tg ~ -60ºC
Tg ~ -120ºC
POEM
poly (dimethyl siloxane)
PDMS
Free Radical Synthesis- macromonomer route - scalable & cheap- no catalysts, no impurities
Graft Architecture- improved mech. properties
High MW PDMS macromonomers- low Tg: high conductivity- microphase separation:
rubbery solid- silicone component:
good T stability
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POEM-g-PDMS
σ > 1×10−5 S/cm
conductivity comparable to that of pure POEM liquid microphase separation confers
good mechanical properties
cond
uctiv
ity (S
/cm
)
1.00E-06
1.00E-05
1.00E-04
1.00E-03
2.7 2.9 3.1 3.3 3.5
1000/T
97ºC 25ºC
POEM liquid
POEM-g-PDMS 70:30 solid
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TEM of POEM-g-PDMS
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thermal stability of POEM-g-PDMS
thermally stable up to 300°C facilitating battery integration, e.g., soldering & sputtering operations
Steven Dallek, NSWC Carderock
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GCE stable beyond 5 V
GCE
-2
-1.5
-1
-0.5
0
0.5
1
1.5
2
0 1 2 3 4 5 6
voltage vs Li⏐Li+ (V)
curr
ent (μA
/cm
2 )
22ºC
GCE + LiCF3SO3
voltage vs Li⏐Li+ (V)
22ºC
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cycling behavior of GCE thin-film cell
1.5 - 4.0 V, ic = id = C/2, room temperature
Li / GCE (2μm) / VOx
limited by Li surface roughness (~ 1 μm)
0
50
100
150
200
250
0 50 100 150 200 250
cycle number
capa
city
(mA
h/g)
100% solid-state
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synthesis of fully-dense cathode films
no binderno additive
100% loading
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phase transformation and valuesGITTD~
D varies by almost 100× over range of operation!
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AC cyclic voltammetry
(V)
Quantitative assessment of α and ko
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1.E-03
1.E-02
1.E-01
1.E+00
1.E+01
1.E+02
1.E+03
1.E-14 1.E-13 1.E-12 1.E-11 1.E-10 1.E-09
D (cm2/s)
Dam
kohl
er N
umbe
r .
diffusion-controlled
reaction-controlled
k = 10-7 cm/s
Damköhler number, Dk = (k L) / D
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breaking the one-electron barrier
Today LiCoO2, LiNiO2, LiFe(PO4) all use only one electron per metal (e.g. Co4+/Co3+)
theoretical capacity limited << 300 mAh/g
The Future compounds where metal cycles over multiple redox steps
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breaking the one-electron barrier
In the presence of Mn,
Li+ + 2e- + LiXNiO2 Li1+XNiO2
Li+ + 2e- + Ni4+ Li+ + Ni2+
cathode:
Pb4+ + 2 e− Pb2+ (redn)anode:
Pb0 Pb2+ + 2e− (oxidn)
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breaking the one-electron barrier
theoretical capacity
≈ 600 mAh/g !
≈ 540 Wh/kg !
two-electron change around Ni upon Li intercalation
In the presence of Mn,
Li+ + 2e- + LiXNiO2 Li1+XNiO2
Li+ + 2e- + Ni4+ Li+ + Ni2+
G. Ceder, MIT
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breaking the one-electron barrier
theoretical capacity ≈ 1000 mAh/g !
≈ 700 Wh/kg !
Li+ + 3e- + LiXCrO3 Li1+XCrO3
Li+ + 3e- + Cr6+ Li+ + Cr3+
Your wildest dream
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thin-film batteries: fully-dense cathodes
multilayer, flexible laminate
fully dense oxide cathode (0.5 µm)
solid polymer electrolyte (1.0 µm)
metallic lithium anode (0.37 µm)
400 Wh/kg (700 Wh/L) & 650 W/kg (1.1 kW/L)
thin-film battery
fully dense oxide cathode solid polymer electrolyte
metallic lithium anode
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battery performance metrics
x MIT SPB
RagonePlot
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So where are we?
not ready for electrification just yet
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Learning to crawl before walking
flexible solar cell
flexible battery
flexible necktie
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Here is another prototype sLimcell
The Thin ManThe Thin Man™™
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It’s a tough way to make a living
application price point
communications $1,000 / kWh
automobile traction $100 - 200 / kWh
laptop computer $5,000 - $10,000 / kWh
severity of service conditions price
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Prediction is very difficult, especially about the future.
- Niels Bohr
What can we expect?
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observations & opinions
One size does not fit all: different applications call for different power sources tailored designs
Batteries have been around for a long time:user community justifiably frustrated at state of battery development and rate of progress
Big changes are under way:ingress of materials scientists invigorating the field
computational materials science acceleratingthe rate of discovery – knowledge limited
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acknowledgments
Office of Naval ResearchOffice of Naval Research
MIT MRSEC (NSF)MIT MRSEC (NSF)
GerbrandGerbrand CederCeder, Anne M. Mayes,, Anne M. Mayes,P.E. P.E. TrapaTrapa, E.A. Olivetti, and S.C. , E.A. Olivetti, and S.C. MuiMui