electrochemical energy storage and extended-range electric...
TRANSCRIPT
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Electrochemical energy storage and extended-range electric vehicles
Mark VerbruggeDirector, Materials and Processes Lab
General Motors Research & Development Center
National Science Foundation workshop: “Drug Discovery Approach to Breakthroughs in Batteries,” 8-9 September 2008.
Saturn Vue10 ZEVPlug-in HEV
Volt concept40 ZEVExtended-range EV
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Outline
• Automotive trends and technology drivers
• GM roll-out plan for
– Hybrid Electric Vehicle (HEV)
– Plug-In Hybrid Electric Vehicle (PHEV)
– Extended Range- Electric Vehicle (EREV)
– Fuel Cell Electric Vehicle (FCEV)– Fuel Cell Electric Vehicle (FCEV)
• EFlex Rechargeable Energy Storage System (RESS)
– Requirements, Status, Outlook
• How might we address battery life issues…a research problem
• Summary
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OpportunityOpportunity
Personal vehicles: a growth industry
– 2007: 71M sales
– 2017: 98M sales
Personal vehicles: a growth industry
– 2007: 71M sales
– 2017: 98M sales
Challenge: SustainabilityChallenge: Sustainability
–Energy – Safety
–Environment – Congestion
–Energy – Safety
–Environment – Congestion
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Advanced Propulsion Technology Strategy
ImprovedVehicle
Fuel Economyand
Emissions
DisplacePetroleum
Hybrid ElectricHybrid ElectricVehicles (including
Extended Range Extended Range Electric Vehicles
HydrogenFuel Cell Vehicles
HydrogenFuel Cell Vehicles
EFlex
)EnergyDiversity
Bio Fuels (Ethanol E85, Bio-diesel)
Petroleum (Conventional & Alternative Sources)
Near-Term Mid-Term Long-Term
Electricity (Conventional & Alternative Sources)
Hydrogen
Hybrid ElectricVehicles (including
Plug-In HEV)IC Engine
and TransmissionImprovements
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Common drivetrain system uses electricity created and stored on-board the vehicle
Engine-generator
Hydrogen fuel cell
Advanced battery
Common drivetrain system uses electricity created and stored on-board the vehicle
Engine-generator
Hydrogen fuel cell
Advanced battery
GM E-FlexGM E-Flex
Advanced battery
Plug-in capable
Electricity can be generated from a wide range of energy sources
E-Flex enables energy diversity
Advanced battery
Plug-in capable
Electricity can be generated from a wide range of energy sources
E-Flex enables energy diversity
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Extended-Range Electric Vehicle (E-REV)Extended-Range Electric Vehicle (E-REV)
120kw electric motor120kw electric motor
Powers front wheels
Powers front wheels
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Extended-Range Electric Vehicle (E-REV)Extended-Range Electric Vehicle (E-REV)
16 kilowatt-hour lithium-ion battery pack16 kilowatt-hour lithium-ion battery pack
Stores electricityfrom the gridStores electricityfrom the grid
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Extended-Range Electric Vehicle (E-REV)Extended-Range Electric Vehicle (E-REV)
74 Hp engine
53 kW generator
74 Hp engine
53 kW generator
E-Flexrange-extender
Creates electricityon-board
E-Flexrange-extender
Creates electricityon-board
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Extended-Range Electric Vehicle (E-REV)Extended-Range Electric Vehicle (E-REV)
E-REV charge portsE-REV charge ports
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30%
40%
78% of customers commute 40 miles or less daily
78% of customers commute 40 miles or less daily
40 Miles Is the Key
40 Miles Is the Key
Typical One-Way Miles From Home To WorkTypical One-Way Miles From Home To Work
0%
10%
20%
1-5 6-10 11-15 16-20 21-25 26-30 31-35 >35
Based on OmniStats Data posted by the U.S. Bureau of Transportation
MilesMiles
KeyKey
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GM’s PortfolioGM’s Portfolio
Emphasis for today’s talk
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Rechargeable Energy Storage System (RESS) for the EFLEX program
Two System Suppliers contracts were awarded (June 2007):
• Compact Power Inc. (CPI) subsidiary of LG Chem
– Integrating LG Chem cells
• Continental Automotive (Conti)
– Integrating A123 Systems cells
Cell development contract awarded to A123 Systems (Aug 2007)
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EFLEX RESS Test Status
Tested successfully on pack level
• Power
• Energy
• Efficiency
• Thermal systems
• Controls
GM Lab Warren, Michigan
• Controls
Tested successfully on the cell level
• All of the above
• Accelerated Life
• Abuse
GM Lab Mainz-Kastel, Germany
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Extended Range Electric VehicleOperation Modes
Sta
te o
f C
harg
e
(SO
C)
100 %
Electric Vehicle Mode
Engine off = Charge Depletion
Extended Range Mode
Engine-Generator on (off)= Charge Sustaining
Park Mode Charge Mode
Electric on-board chargerfor (electric) grid power
Park Mode
Usable Energy
Sta
te o
f C
harg
e
(SO
C)
Time
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Usable Energy definition
Powerfor 10s
Discharge Power (BOL)
Usable Energy Range (Begin of life, BOL)
Discharge Power (EOL)
Usable Energy Range (End of life, EOL)
For the Chevy Volt, the requirement for usable energy is 8kWh (EOL).
Depth of Discharge
Charge Power Requirement
Charge Power (BOL)Discharge Power Requirement
Charge Power (EOL)
Usable Energy is defined by the operating range over which the charge and discharge power requirements are fulfilled at end of life (Battery Temperature:
20°C). This enables predictable vehicle performance in EV mode.
Full Battery Empty Battery
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Discharge
Charge
Po
we
r [k
W]
EFLEX: Power required to drive City Cycle incharge depletion (EV) mode
Charge
VEHICLE speed on km/hr
0
10
20
30
40
50
60
70
80
90
100
0 200 400 600 800 1000 1200 1400
Time [s]
Speed [km/h]
Miles per hour
50
25
Sp
ee
d [
km
/h]
Time [s]
Time [s]
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VEHICLE Speed km/hr
Miles per hour
Power profile in US06 cycle EFLEX charge depletion mode (EV)
Time [s]
Po
wer
[kW
]
Tem
p [
Deg
C]
Discharge
Charge
Cooling off, increase of 2.5 KCooling on, increase of 1 K
US06 drive cycle power profile exceeds the average power of more than 95% of drivers surveyed in a study in California.
0
20
40
60
80
100
120
140
0 100 200 300 400 500 600
Time [s]
Speed [km/h]
Miles per hour
75
62
50
38
Sp
eed
[km
/h]
Time [s]
Length: 12 km, 7.5 miles
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Comparison of GM’s requirements to USABC specs
Characteristics at EOL (End of Life)High Power/Energy
Ratio Battery
GM 2-Mode PHEV
(EFLEX FCEV)
High
Energy/Power
Ratio Battery
EFLEX
EREV
Reference Equivalent Electric Range miles 10 10 40 40
Peak Pulse Discharge Power - 2 Sec / 10 Sec kW 50 / 45 50/45 46 / 38 115/110
Peak Regen Pulse Power (10 sec) kW 30 27 25 60
Available Energy for CD (Charge Depleting) Mode, 10 kW Rate kWh 3.4 3.5 11.6 8
Available Energy for CS (Charge Sustaining) Mode kWh 0.5 0.3 0.3 0.35
Minimum Round-trip Energy Efficiency (USABC HEV Cycle) % 90 90 90 90
Cold cranking power at -30°C, 2 sec - 3 Pulses kW 7 7 7 8
Requirements of End of Life Energy Storage Systems for PHEVs
EFLEX EREV requires 2.5 times the power ofUSABC requirements
CD Life / Discharge Throughput Cycles/MWh 5,000 / 17 5,000 / 58 4700 / 54
CS HEV Cycle Life, 50 Wh Profile Cycles 300,000 300,000
Calendar Life, 35°C year 15 10 15 10
Maximum System Weight kg 60 90 120 160
Maximum System Volume Liter 40 TBD 80 100
Maximum Operating Voltage Vdc 400 420 400 410
Minimum Operating Voltage Vdc >0.55 x Vmax 170 >0.55 x Vmax 232
Maximum Self-discharge Wh/day 50 50 5% in 60 Days
System Recharge Rate at 30°C kW 1.4 (120V/15A) 1.4 1.4 (120V/15A) 3.6 (230V/16 A)
Unassisted Operating & Charging Temperature Range °C -30 to +52 -30 to +52 -30 to +52 -30 to +52
Survival Temperature Range °C -46 to +66 -46 to +66 -46 to +66 -46 to +66
Maximum System Production Price @ 100k units/yr $ $1,700 $3,400
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Batteries for extended range EV’s and plug in Hybrids…future focus
Cost
• Can we size pack closer to end-of-life requirements?
• Can we reduce materials & processes costs?
Life
• How do electrodes fail?
• Can we develop an accelerated life test?
Temperature tolerance
• Can we improve low temperature power?
• Why is battery life shorter at higher temperatures?
1
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Research questions around degradation around degradation phenomena
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What governs the durability and reliability of lithium ion cells? Reactions, transport phenomena, and fracture within insertion electrodes.
Mark Verbruggewith YT Chengand many others inside and outside GM
Playa with mud cracks, dawn. Black Rock Desert, Nevada, USAhttp://www.terragalleria.com/pictures-subjects/dried-mud/picture.dried-mud.usnv9106.html
Crack (fracture) propagation takes place during drying (moisture extraction) when the surface undergoes tensile contraction.
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+Li
]S[Li S, ,e −+− − δδ
Intercalation process
Typically 10% expansion for negatives (carbons) and 5 to 10% for positives (metal phosphates or oxides)
]S[LieSLi −+−+ −=++ δδ
Negative (carbon) charge
Negative (carbon) discharge
expansion
contraction
phosphates or oxides)
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NEGATIVEELECTRODE
SEM images of the surface of the KS-15 composite pristine electrode(a) and the same electrode after 140 intercalation–deintercalation cycles at 25 C (b and c).
During cycling, graphite particles crack into smaller pieces that are less oriented than the original platelets, with the possible filling of the cracks thus formed by the reduction products of the electrolytesolution. In addition, the average crystalline size (estimated by Raman spectroscopy) decreases as cycling progresses.
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NEGATIVEELECTRODE
Video Clip Video Clip
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“This result indicates volume change causes the increase
POSITIVEELECTRODE
causes the increase in resistance.”
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POSITIVEELECTRODE
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POSITIVEELECTRODE
Cycles0’ 010 3060 60_p1
60_p2
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Wöhler S-N curve (1870…railroad axles)
Stress
Time Ultimate goal: Determine the endurance limit (cycle life) for insertion electrodes by comprehending the periodic
MaximumStressAmplitude
Number of cycles
Endurance or fatigue limit?
comprehending the periodic stress
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S-N curves as ∆∆∆∆SOC-N curves
SOC(~stress)
TimeEV0.9
As presented, this
∆∆∆∆SOC
Maximum
∆SOC(Faradaic)
Number of cycles
EREV
1,000 5,000 300,000 750,000
0.7
0.10
HEV
As presented, this interpretation does not address temperature and chemical degradation issues.
Supercapacitor
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What’s wrong with cracks?Overall qualitative degradation model…Li-carbon
++→+ ...gassesSEIO-H-RS]-[Li
Cracks
Expanded view of surface
SEI forms on newly exposed surfaces (cracks)
↑=+↓+→+ 223 CHCHLiCO S S]-[Li
Increased disorder. d002 peak-width at half max amplitude increases with time for lithiated carbon
1. Loss of Li: SEI formation and loss of Li seen in full cell experiments
2. Electrode isolation and loss of active material when cracks join
No firm experimental confirmation to date, but consistent with observations
Cracks via cycling
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Mathematical detailsPotential step, Θ0 → ΘR
r
θ
Radius RR
K
E
RS
R
K
E
R
K
ESss
s
2)21(1
2
, 2)21(
1
)1(1
0
21 ν
τ
ν
ν
−+
−=−
+
+−
=
Surface modulus Ks Surface stress τ0
Influence of both terms vanish as R → ∞
Results now consistent with nano-particle and thin film electrodes yielding enhanced cycle life
For the stress functions, the transient terms are proportional to ∆∆∆∆SOC (∆∆∆∆SOC ∝∝∝∝ stress)
( ) ( )232
1
1
0
1
2
132
10
1
)1(3sin)1(
)(
cos sin )1(
)(
2 )(2
)1(3
2),(
)1(3
)1(3
)(
)( cos )(sin )1(
)()(4
)1(3
2),(
)1(3
22
22
SCExn
xn
xn
xnx- nxn
n
Se
SrtCE
SCE
exn
xnx- nxn
n
S
SrtCE
S
nn
n
n
R
R
S
S
n
n
n
R
Rr
S
Ω−
+
−+−−Θ−Θ−
−Θ=Ω−
Ω−
+
−+Θ−Θ−
−Θ=Ω−
∑
∑
∞
=
−
−∞
=
νπ
ππ
ππππ
σν
νπ
ππππ
σν
τπ
θ
τπ
cycle life
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On surface energy and surface stress
J. Willard Gibbs, H. A. Bumstead, W. R. Longley, R. G. Van Name, The Collected Works of J. Willard Gibbs, Longmans, Green and Co., 1928.
• Pioneering work on surface thermodynamics
R. Shuttleworth, Proc. Phys. Soc. London, Ser. A, 63 (1950)444.
• Relates surface stress to the work of formation of an elastically strained surface
J. C. Eriksson, Surf. Sci., 14(1969)221.
• Gibbs-Eriksson equation…generalized surface thermodynamics
B.M. Grafov, G. Paasch, W. Plieth, A. Bund, Electrochim. Acta, 48(2003) 581.B.M. Grafov, G. Paasch, W. Plieth, A. Bund, Electrochim. Acta, 48(2003) 581.
• Unifying treatment for Shuttleworth equation for the elastic spherical electrode with the Laplace formula and the Gibbs adsorption equation
P. Sharma, S. Ganti, and N. Bhate, Appl. Phys. Lett., 82(2003)535, 89(2006)049901.
• Boundary condition used in this work,
Helpful related texts
D. Maugis, Contact, Adhesion, and Rupture of Elastic Solids, Springer, 1999.
J. Newman and K. E. Thomas-Alyea, Electrochemical Systems, 3rd ed., Wiley, 2004.
θφθ ετσσ ssurfsurfK+== 0
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Next steps on life modeling
Crack initiation and propagation within a particle
• A difficult problem even in the absence of electrochemical phenomena
• Flaw distributions within electrode particles?
• Primary particles, potentially with grains, and secondary particles (agglomerates)
• Incorporate the influence of chemical degradation 2• Incorporate the influence of chemical degradation processes
• How does temperature come into play?
– Mechanical deformation within particles is not substantially affected by the limited temperature fluctuations
– Chemical reactions rates are thermally activated
Last, scale up from individual particles to porous electrodes
2
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Details
Model equations
Plots of intercalate and Plots of intercalate and stress distributions
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Surface Mechanics. ( ) θθθφφθθθ ετελµτσσσ ssssurfsurfsurfK+≡++==≡ 00 2 ,
where ( )sssK λµ += 2 is known as the “surface modulus.” For mechanical equilibrium,
( )R
Rrsurf
r
θσσ
2−=→
( )
( )[ ] CE
CE
r
rr
Ω+−−=
Ω+−=
3
11
1
3
12
1
νσσνε
νσσε
θθ
θ
Solid Mechanics
22 ∂+
∂=
∂ yyy
2R
Dt=τ ,
R
rx = , and
0
0
0
0 ),(),(
Θ−ΘΘ−Θ
=−
−=
RR
rt
CC
CrtCy
Intercalate (lithium) transport
dr
dur
=ε and r
u=θε .
02 =−
+rdr
drr θσσσ
dr
dC
r
u
dr
du
rdr
ud
31
12222
2 Ω
−
+=−+
νν
Er
3θθ
0
1)1,(
0),0(
2
0
2
=∂∂
=
=∂∂
+∂∂
=∂∂
=xx
y
ty
xy
x
y
xx
yy
τ
0)0( =u
These coupled equations can be solved analytically.
r
θ
Radius R
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Positive stress: tension. Negative stress: compresion.
Charge (lithiation) of negative (carbon) electrode
Conventional surface conditions
Maximum tensile (radial) stress at the particle center at ττττ = 0.0574
• No concentration gradients initially and at end of charge
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Charge (lithiation) of negative (carbon) electrode
Conventional surface conditions
Max (hydrostatic) tensile stress at the particle center
Max shear stress and circumferential compressive stress at the surface initially
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-1.5
-1
-0.5
0
0.5
Rad
ial
stre
ss
3(1
−ν) σ
r/E
Ωc S
K s , N/m
-5
0
5
R = 1 nm
2
5
10
20 50
τ = tD /R2 = 0.0574
K s = 0 unless otherwise indicated-2
-1.5
-1
-0.5
0
0.5
Cir
cum
fere
nti
al s
tres
s 3
(1−ν
) σθ/
EΩ
cS
τ = tD /R2 = 0.0574
τ0 = 1 J/m
2
K s = 0
R , nm
infinite
50
20
10
5
2
1
Charge (lithiation) of negative (carbon) electrode
Influence of surface mechanics are quite significant
• Radial stress transformed from tensile to compressive
• Similar influence on tangential (circumferential) stess
Note: it is more challenging to make electrodes with smaller particles…enhanced stability comes with a cost
-2
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Radial position r/R
K s = 0 unless otherwise indicated
τ0 = 1 J/m
2
-2.5
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Radial position r/R
K s = 0
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Summary
• Automotive trends and technology drivers
• GM HEV (hybrid electric vehicle) and EREV (extended-range electric vehicle) roll-out planroll-out plan
–Eflex/Volt Rechargeable Energy Storage System for extended range electric vehicles
• A look towards understand battery life degradation issues