1m

Polymer Separator Films

for Lithium Ion Batteries:
Past, Present, and Future
Patrick Brant
ExxonMobil Chemical Company
University of Tennessee
Knoxville, TN
March 4, 2010
2
Overview
ExxonMobil organization
Plastics - Polyolefin utility
Catalytic olefin polymerization with metallocenes
Gas phase polymerization process
Lithium ion batteries and separator film
Summary
Early / Lead Generation Pre-development Development
3
4
POs Key Features
Polyolefins (POs) Champions of Thermoplastics
a
Chemically Inert
Low cost
Recyclable / Energy
Recovery
Exceptional Fabrication &
Applications Versatility
WW Production of Thermoplastics > 350 Billion Pounds / Year
POs > 50% of all Thermoplastics
Sustainable? 6-7%, CO
2
[2 saved/1 produced]
b
, downgauging
Paper or plastic? 4x more
POs
54%
PS 9%
PVC
17%
PET 5.0%
ABS
3.5%
PU
5.5%
PA
1.3%
PMMA
0.9%
PC
0.9%
a
G. Gottfreid, Polymeric Materials, Ch. 1
b
McKinsey and Company study, reviewed
by the ko Institute
Others
5
Polyolefins in Transportation
About 200 lb of plastics, rubber in typical car
10% Weight Reduction
6.6% Fuel Economy
Advanced motor oils
6
Example of Metallocene Catalyst Impact
Commercialization Challenge
Introduce new catalyst on world scale
UNIPOLgas phase PE reactor
Metallocene catalyst + methylalumoxane
activator + porous silica support
2000 g PE/ g catalyst + complex formulation
makes catalyst expensive
Reactor difficult to start and fouls out / sheets
Solutions
Simplified catalyst formulation
Careful control of poisons
Right choice of poison scavenger
Right choice of operability aids/additives
Avoid making polymer death grades
Results
Productivities improved to >6000 g PE/ g
catalyst and higher
Stable commercial operations
Less waste, fewer resources
Strong business growth (~30%/year) of
polymers that sell for significantly higher
prices
< 500 psi, < 110 C
Huge reactors
> 7000 ft
3
, >400 Kta
residence time 3 hr
Low conversion of
monomer per cycle
Cooler
Compressor
Monomer
Polymer
Discharge
Catalyst
P
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G
r
a
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s

Bed weight:
125T = 727+
Heat removal:
94.5 kJ/mol or
22.6 kcal/mol
Reactor data:
<500 psi <100 C
>7000 ft
3
>400 kTA
Residence time ~ 3 hr
7
Granule Morphology One Key to G Reactor Operation
Neat granules
(stereomicroscopy)
Void morphology of granules
(oil immersion)
Surface & cross-sectional
views of granules (SEM)
Replication
Particle Diameter
P
o
p
u
l
a
t
i
o
n
Time
Epoxy
Thin section of granule iPP
followed by HDPE (TEM)
white = HDPE, gray = iPP
What happens to the catalyst?
8
Polyethylene A High Performance Polymer
C
C
C
C
C
H H
H H
H H
H H
H H
Battery Separator Film
9
Lithium Ion Battery Overview
Past Present
Motivation for work
Battery components and brief history
Separator structure and functions; how they are made
Lithium ion battery benefits, impact
Future
Drivers
Opportunities
EV, HEV, pHEV considerations
Summary
10
Initial Motivation for Work
Two clear fundamental advantages
1. Lithium is the lightest metal
2. Lithium half reaction standard electrode potential is big

In principal, fundamental advantages could lead to

Higher energy density; weight and volume advantage
Higher power density at a given energy density
Fewer cells, related parts
Key Hurdles- beginning in 1975
Cathode
Anode
Electrolyte
Separator
Self-discharge performance
Memory
Cost per W-h and per W
Abuse resistance
Cold/hot behavior
Thermal management (safety)
Cycle life
Markets?

Electrochemical Series in Handbook of Chemistry and Physics

Ragone Plot
1
10
100
1000
10000
1 10 100 1000
Specific Energy (Wh/kg)
S
p
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c
i
f
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P
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(
W
/
k
g
)LIB
Other
Battery
Options
* 1 Wh = 3,600 J or 860.4 cal
11
Basic Components in (Lithium Ion) Battery

ion transport
* Separator = Battery Separator Film = BSF
Separator *
Anode
Cathode
Electrolyte
Graphitic Carbon Lithium Metal Oxide
e
-

And in all batteries

Galleries for Li
ion transport
12
Brief History
Other Cathodes:
Li(Ni,Mn,Co)O
2
Li(Ni,Co,Al)O
2
F. Beguin and R. Yazami, Actualite Chimique 2006 295-296, 86-90
G
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O
2
13
Separator Film Requirements
Permeable (~40-50% void volume) for ready ion
transport, yet insulate electrodes
Small pores but low resistance
Chemically inert, uniform, free of flaws
2-10+ years in highly reactive environment
Excellent puncture strength
Thin (7-30), dimensionally stable
Slitting, compatible w/ manufacturing equipment
Act as safety device if cell becomes too hot
Safety margin: = [meltdown temperature
shutdown temperature]
The higher the meltdown temperature the better
Lithium dendrite
Porosity
y Tortuousit
p
eff
R
14
How to Make a Classic Monolayer Separator Film
Pennings et al, 1965 - 1979: Gel spinning and super drawing of uhmw HDPE filaments
Solution of polyethylene dissolved in hydrocarbon
Gel sheet
Thin wall cellular structure composed
of stacked lamella crystals
Micro-porous film
Uniform fine fibrous network
composed of stacked lamella crystals
Biaxial Biaxial
orientation, orientation,
extraction extraction
1m 5m 1m
SEM SEM TEM TEM 5m
5m
Collapse of Collapse of
cell cell
Fibrillation of Fibrillation of
plane stacked plane stacked
lamella crystal lamella crystal
Cell Cell
Schematic
diagram
~ 1 ~ 1 m m ~10nm ~10nm
AFM
1m
15
A Closer Look at Separator Morphology
TEMs of stained cross-sections show highly uniform, finely textured morphology
TD x ND plane MD x ND plane
T
D
N
D
M
D
N
D
M
D
T
D
16
Orientation and Crystallinity
Sample 1: 2 % UHMWPE
0
50
100
150
200
250
300
350
400
450
8 13 18 23
2 (
o
)
I
(
2

)

(
a
.
u
)
WAXS of a BSF
(110)
(200)
a
b
b
c
a
ORTHORHOMBIC
UNIT CELL:
a = 7.36
b = 4.92 A
c = 2.54 ; chain axis
(110) (200)
Use of the National Synchrotron Light Source, Brookhaven National Laboratory, was supported by the U.S.
Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-
98CH10886
17
Realizing the Benefits of Lithium Ion Batteries
Higher energy density - nearly 2x higher than Ni-MH; weight advantage
Higher power density at a given energy density
Higher voltage - ~3.6 V vs 1.2 V for Ni-Cd and Ni-MH; fewer cells, connections
Better self-discharge performance - around one tenth of Ni-Cd and Ni-MH
No memory effect
Expect lower cost per W-h and per W
Raw material cost can be a big factor
Other key data:
Abuse resistance
Cold/hot behavior (-40 to +40C)
Thermal management
Cycle life
18
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1
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^
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Y e a r
Growth of LIB Comes with Increasing Demands
Markets: Cellphone, laptop, camcorder, digital camera, power tool, ebikes,
Increasing capacity
Downgauging / higher strength
Early Li-ion
Battery at EV show
Chicago, 77
Invention of
microporous
PE separator
Separator used in
worlds first LIB
1
2
3
1990 1995 2000 2005 2010
A
h
HEV HEV
EV EV
Electrovaya Electrovaya s s Maya Maya- -300 300
220 Ah
14 Ah
1 Ah
4000+ Ah
70 Ah
19
Future Continuing Growth
Energy and LIB
Opportunities, challenges
EV, HEV, pHEV considerations
Evolving demands on separator
Economy Security
Climate
6 x10
9
Tons CO
2
/year
Energy
WSJ, August 6, 2009
20
Transportation - Global
Power
Generation
1.6%
Res/Comm
0.4%
Industrial
1.0%
Transportation
1.4%
84.5
40.4
124.0
61.5
2030: ~310 MBDOE
1.2%
demand by sector
2030 demand in MBDOE
Average growth/Yr 2005-2030
0
10
20
30
40
50
60
70
1980 2005 2030
Light-Duty
Vehicles
Heavy Duty
Aviation
Marine
Rail 0.7%
2.5%
0.3%
2.0%
1.9%
0
10
20
30
40
50
60
70
1980 2005 2030
Light-Duty
Vehicles
0.3%
global transportation
by sub-sector
MBDOE Average Growth / Yr.
2005 2030
1.4%
21
Gasoline ~ 25 cents / gallon
22
Batteries in Transportation
10
0
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1
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2
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3
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7
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(
W
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k
g
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0.01 0.1 1 10 100 1000
Specific Energy (Wh/kg)
C
a
p
a
c
i
t
o
r
s
Batteries
Fuel
Cells
Combustion
Electrochemical
Capacitors
Engines
E
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Ragone Plot
LIB
~0.4-0.5
b
0.9 Efficiency of
Producing Fuel
85-90% * ~15-20% * Energy Efficiency
0.17 * 13
a
* Energy Density,
kWh

/kg
LIB Gasoline
Diversification and more efficient use of hydrocarbons: 13.8 MBbl oil/day for transportation in US
Reduce carbon dioxide emissions
Part of integrated set of solutions
a
3x the energy density of sugar
b
For production of e
-
from coal or NG

1 kWh = 3,600 kJ or 860.4 kcal

Gasoline versus LIB
* Deutsche Bank, Auto Manufacturing Electric Cars: Plugged in, 9 June 2008
23
Relative LIB Benefit / Cost
Rough estimate: LIB size for EV ~200 kg (80 -1,000 V)
% of Work Done by
Batteries
[
B
e
n
e
f
i
t

/

C
o
s
t
]
1 = break even
high
energy
high
power
HEV
EV
Drive Cycle
V
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t
y
H
E
V
H
E
V
IC
EV = 100% of cycle
HEV < 100%
Energy capture
24
Evolving Separator Demands
Higher temperature stability - ~ 200-250+C
Retain sufficient dimensional stability
Coatings and higher temperature polymers
Blends, co-extrusion
Increasing puncture resistance
w/ appropriate permeability
Lower shutdown temperature
~10+ year life
Delivered flawlessly at lower cost
for larger battery formats, and bigger battery packs.
but emphases vary according to LIB chemistry and module
or pack control
Co-extruded Separator
Monolayer
Wet
Process
Wet
Process
Coex
Technology
Coex
Technology
Polymer
Design
Polymer
Design
25
Improved Thermal Stability
: E25MMS (mono-layer)
: New Commercial Grade (co-extruded)
Permeability
Puncture
Thermal
Stability
Shutdown
Temperature
Meltdown
Temperature
Power
Mechanical
Safety
Thermal
Safety
Tensile
Balance
New commercial grade has superior thermal stability, higher permeability
and meltdown temperature than standard mono-layer
26
Lower TD Shrinkage
TD Shrinkage
0
10
20
30
40
E25MMS V25EKD V25CGD Developmental grade 1
Grades
%

s
h
r
i
n
k
a
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e

TD shrinkage at 105'C, 8 hrs TD shrinkage at 130'C, 30mins
Lower TD shrinkage allows
more flexible LIB designs
27
Summary
Lithium ion batteries power the portable electronics revolution
Polyolefin separators a key part of this success story
Lithium ion batteries for transportation: ebikes, EV/p-HEV, HEV
Major commitments already
Battery and auto manufacturer announcements
Continuing improvements, especially to reduce cost
Once again, separators critical to performance
Can be a key part of overall drive to increase energy efficiency
Uninterrupted power supplies
Continuing technology breakthroughs are critical
Exciting research and development opportunities
28
Thank you
Many contributors to this talk
JoAnn Canich, Alan Vaughan
Koichi Kono, Jack Tan, Takeshi Ishihara, Jeff Brinen, Zerong Lin, ..
29
Shutdown Performance
0
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100
150
200
100 110 120 130 140
Temperature /
o
C
P
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a
b
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y

(
r
e
l
a
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i
v
e
)
Developmental
grade 2
V25EKD
Developmental grade 2 is designed for earlier pore closure with complete
shutdown at 128C, potentially prevent exothermic reaction which leads
to thermal runaway in the event of internal shorts or overcharging
30
Economics Lesson: Hybrid Sales Linked to Fuel Price
U.S. Gasoline Price and Hybrid Sales (2004-2008)
0.00
0.50
1.00
1.50
2.00
2.50
3.00
3.50
4.00
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(
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g
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0
5,000
10,000
15,000
20,000
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35,000
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50,000
N
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A
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Gas Price HEV Sales
US accounts for ~70% of all HEV sales