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Models for Battery Reliability and Lifetime
Applications in Design and Health Management

Kandler Smith
Jeremy Neubauer
Eric Wood
Myungsoo Jun
Ahmad Pesaran
Center for Transportation Technologies and Systems
National Renewable Energy Laboratory

NREL/PR-5400-58550
Battery Congress April 15-16, 2013 Ann Arbor, Michigan
NATIONAL RENEWABLE ENERGY LABORATORY
Better life prediction methods, models and management
are essential to accelerate commercial deployment of Li-
ion batteries in large-scale high-investment applications
2
End User Goals:
Understand reliability and economics of new technologies
(e.g., electric-drive vehicles vs. conventional vehicles)
Manage assets for maximum utilization
(e.g. route scheduling, charge control to optimize EV fleet life and cost)
OEM Goals:
Optimize designs
(size, cost, life)
Minimize business &
warranty risk
Reduce time to
market
*Source:
MarcIsaacson,
LockheedMartin
Time-to-market vs acceptable risk for satellite battery industry*
NATIONAL RENEWABLE ENERGY LABORATORY
NREL Research & Development Addressing
Battery Lifetime
3
No cooling
Air cooling
Air cooling,
low resistance ce
Phoenix, AZ ambient conditions
Liquid cooling
Life predictive modeling and battery
system tradeoff studies
Computer-aided engineering of
batteries (CAEBAT program)
Battery health estimation & management
(Laboratory-Directed R&D program)
Battery prognostic and electrochemical
control (ARPA-E AMPED program)
Life scenario
analysis
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3D Multi-
physics
simulation
Aging
model
Online & offline health
tracking of real-world
applications
Advanced battery
management R&D with
industry & university
partners
NATIONAL RENEWABLE ENERGY LABORATORY
Outline
4
Part 1: Battery Life Modeling
Life Model Framework
NCA Model
FeP Model
Part 2: Life Model Application
Life-Cycle Analyses
Real-Time Health Management
NATIONAL RENEWABLE ENERGY LABORATORY
NREL Life Predictive Model
Relative
Resistance
Relative
Capacity
Data shown above: J.C. Hall, IECEC, 2006.
Q
sites
= c
0
+ c
2
N Q
sites
= c
0
+ c
2
N
R = a
1
t
1/2
+ a
2
N
Calendar fade
SEI growth (possibly
coupled with cycling)
Loss of cyclable lithium
a
1
, b
1
= f(DOD,T,V)
Q = min ( Q
Li
, Q
sites
)
Q
Li
= b
0
+ b
1
t
1/2
+ b
2
N Q
Li
= b
0
+ b
1
t
1/2
+ b
2
N
Cycling fade
Active material structure
degradation and
mechanical fracture
a
2
, c
2
= f(DOD,T,V)
5
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(
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Time (years)
r
2
= 0.942
Li-ion NCA chemistry
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G
r
o
w
t
h

(
m

)
Arrhenius-Tafel-Wohler model
describing a
2
(DOD,T, V)
NCA
NATIONAL RENEWABLE ENERGY LABORATORY
Life model framework: Graphite/NCA example
6
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NCA
A. Resistance growth during storage
Broussely (Saft), 2007:
T = 20C, 40C, 60C
SOC = 50%, 100%
B. Resistance growth during cycling
Hall (Boeing), 2005-2006:
DoD = 20%, 40%, 60%, 80%
End-of-charge voltage = 3.9, 4.0, 4.1 V
Cycles/day = 1, 4
C. Capacity fade during storage
Smart (NASA-JPL), 2009
T = 0C, 10C, 23C, 40C, 55C
Broussely (Saft), 2001
V = 3.6V, 4.1V
D. Capacity fade during cycling
Hall (Boeing), 2005-2006: (see above)
Data
1. Fit local model(s)
2. Visualize rate-dependence on
operating condition
3. Hypothesize rate-law(s)
4. Fit rate-laws(s)
5. Fit global model(s)
Regression
(
(

|
|
.
|

\
|

=
ref
a
T
T t T R
E 1
) (
1
exp u
(
(

|
|
.
|

\
|
=
ref
ref
oc
V
T
V
t T
t V
R
F
) (
) (
exp
o
u
|
u
|
|
.
|

\
|
A
A
=
A
ref
DoD
DoD
DoD
NCA
PHEV10
Phoenix
Predictive model
Select model with best statistics
NATIONAL RENEWABLE ENERGY LABORATORY
Knee in curve important for predicting end of life
7
Example simulation:
1 cycle/day at 25C
50% DOD:
Graceful fade
(controlled by lithium
loss)
(Hypothesis based on observations from data)
80% DOD:
Graceful fade
transitions to sudden
fade ~2300 cycles
(transition from lithium
loss to site loss)
Life over-predicted by 25% without knee
NCA
NATIONAL RENEWABLE ENERGY LABORATORY
Iron-phosphate (FeP) Life Model
8
Estimated $2M data collection effort of other labs has been leveraged
for this analysis (DOE, NASA-JPL, HRL & GM, Delacourt, CMU, IFP)
Capacity fade with knee region highlighted
FeP
A123 ANR-26650-M1
Li
x
C
6
/Li
y
FePO
4
2.3 Ah, 3.3V
nominal
NATIONAL RENEWABLE ENERGY LABORATORY
Active site loss controlled mainly by
mechanical-driven cycling fade
9
Hypothesis for active site
loss dependence on
operating parameters:
C-rate (intercalation
gradient strains)
DOD (bulk
intercalation strains)
Low T (exacerbates Li
intercalation-gradients)
High T (exacerbates
binder loss of
adhesion)
T (thermal strains)
NATIONAL RENEWABLE ENERGY LABORATORY
Hypothesized Active Site Loss Model
10
Blue symbols are site-
loss rates for each
individual aging
condition
Purple symbols are
global rate-law model
across all aging
conditions
S
i
t
e

l
o
s
s
/
c
y
c
l
e
,

l
o
g
(
c
2
)
( ) ( )| | ( ) ( )( ) . exp exp
, ,
intercal. binder
1 1
R 3 2 1
1 1
, 2 2
)
`

|
.
|

\
|
+ A + =

ref pulse
pulse
ref rate
rate
ref
a
ref
a
t
t
C
C
T T
E
T T R
E
ref
m T m DOD m c c
). , min(
sites Li
q q q =
N b t b b q
z
Li 2 1 0
+ + =
DOD
N c c q
sites 2 0
+ =
accelerated binder
failure at high T
bulk
intercalation
strain
bulk
thermal
strain
intercalation gradient strain, accelerated
by low temperature
FeP
NATIONAL RENEWABLE ENERGY LABORATORY
FeP model comparison with knee data
11
Global model
compared with
13 aging conditions
from
0C to 60C
Active site loss (at room temperature, 1C charge/discharge, 100% DOD reference conditions)
83% due to bulk volumetric expansion/contraction of the active material*
13% due to particle fracture owing to intercalation stress at high C-rates
4% due to temperature swings encountered by the cell
FeP
* This dominant aging term correlates with Amp-hour throughput, often used as a proxy for aging
NATIONAL RENEWABLE ENERGY LABORATORY
Outline
12
Part 1: Battery Life Modeling
Life Model Framework
NCA Model
FeP Model
Part 2: Life Model Application
Life-Cycle Analyses
Real-Time Health Management
NATIONAL RENEWABLE ENERGY LABORATORY
Automotive Analyses: Battery Ownership Model
13
Objective: Identify cost-
effective pathways to reduce
petroleum use and carbon
footprint via optimal use of
vehicular energy storage
systems
Approach:
Trip-by-trip simulation of
hundreds of real-world,
year-long, vehicle-specific
drive patterns in real
climates
Model driver behavior, road
loads, auxiliary loads,
vehicle cabin thermal
response, and battery
electrical, thermal, and life
response
Life
Model
NATIONAL RENEWABLE ENERGY LABORATORY
Minneapolis, MN
Los Angeles, CA
Phoenix, AZ
Phoenix, AZ
Los Angeles, CA
Minneapolis, MN
Minneapolis, MN
Los Angeles, CA
Phoenix, AZ
Phoenix, AZ
Los Angeles, CA
Minneapolis, MN
Automotive Analyses: Battery Ownership Model
14
A recent study of
climate, trip history, and
driver aggression shows
how these factor affect
battery state of health
after 10 years in a
BEV75
- 317 different real-world
trip histories
- 3 different driver
aggression levels
- 3 different climates
- Findings: Climate has
the largest effect on
battery wear, followed
by trip history
NATIONAL RENEWABLE ENERGY LABORATORY
Battery Second-Use Analyses
15
Battery state of health is
critical to determining the
technical capability and
performance of a second-
use battery
Our second-use analyses
incorporate the life model
to calculate a health factor
that becomes a major
determinant in second-use
feasibility
0%
20%
40%
60%
80%
100%
0% 9% 18% 27% 34% 41%
F
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o
f

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P
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n
s
SecondUseHealthFactor
BEV75
PHEV35
(k
H
)
Life
Model
Second-Use
Battery Selling
Price = k
U
k
H
c
N
NATIONAL RENEWABLE ENERGY LABORATORY
Grid Analyses: Community Energy Storage
16
Analyzed the long-term effects of
two different community energy
storage system configurations in a
real-world climate
Tomb configuration: insulated from
ambient temperature and solar
irradiation, strong connection to soil
temperature.
Greenhouse configuration: Strong
connection to ambient temperature, large
effect of irradiation.
Duty Cycle: Daily 60% DOD peak-
shaving event
Climate: Los Angeles, CA
Findings: The difference in long-term
wear between the two system
configurations is small for this
combination of climate and duty cycle
Time (days)
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NATIONAL RENEWABLE ENERGY LABORATORY
Time-scales: Control & Estimation
17
10
-3
10
0
10
3
10
6
10
9
Application
[seconds]
Side reaction limits
Prognostic-
based charging
Control
Prognostic-
based V2G
Available power
Available energy
Particle stress limits
Health
Remaining
life
Embedded
control
NREL PIX 19358
Performance
NREL PIX 19243
Commute
NREL PIX 24515
NREL PIX 20040
NREL PIX 18660
Figure: Dean
Arnmstrong
NREL PIX 10928
Charge
Environment
Grid
2
nd
Use
NREL PIX 20041
NREL PIX 10925
Figures: Vetter, J. Power Sources (2005)
NREL PIX 19243
NATIONAL RENEWABLE ENERGY LABORATORY
Algorithm topology
I,V,T
data
SOH
est
Kalman or particle
filter
Life model
Recursive
regression
SOC
est
Performance
model(s)
RUL
est
Time
Scale
SOP
est
SOP = state of power
SOC = state of charge
SOH = state of health
RUL = remaining useful life
NATIONAL RENEWABLE ENERGY LABORATORY
Diagnostic Example (online)
19
Particle filter + circuit model: Estimates both SOC & capacity within 2% of actual
V
ocv
(SOC,Q)
NATIONAL RENEWABLE ENERGY LABORATORY
Diagnostic Example (vehicle fleet analysis)
20
Date(mm/yy)
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Date(mm/yy)
Figurecredits:EricWood
Diagnostic Analysis Tools also
being applied to
EV MD delivery vehicle fleet
(200+ vehicles, ~1.5 yrs data)
Hybrid fuel cell vehicles
(40 vehicles, ~5 yrs data)
Validation of algorithm with
SCE/Saft Lab Data
Estimation of Total Capacity and DC Resistance using in-service
(partial discharge) I,V,T data
NATIONAL RENEWABLE ENERGY LABORATORY
ARPA-E AMPED: Three Projects
in Battery Management
21
Utah State/Ford
Project: 20% reduction in
PHEV pack energy content
via power shuttling system
and control of disparate
cells to homogenous end-
of-life
NREL: Requirements
analysis; life model of
Ford/Panasonic cell;
controls validation of Ford
PHEV packs
Eaton Corporation
Project: Downsized HEV
pack by 50% through
enabling battery prognostic
& supervisory control, while
maintaining same HEV
performance & life
NREL: Life testing/modeling
of Eaton cells; controls
validation on Eaton HEV
packs
Washington Univ.
Project: Improve available
energy at the cell level by
20% based on real-time
predictive modeling &
adaptive techniques
NREL: Physics-based cell-
level models for MPC;
implement WU
reformulated models on
BMS; validate at cell &
module level
Advanced Management and Protection of Energy Storage Devices
Develop advanced sensing and control technologies to provide new innovations in
safety, performance, and lifetime for grid-scale and vehicle batteries.
NATIONAL RENEWABLE ENERGY LABORATORY
Summary
22
Capable battery life models can be built today, but rely
heavily on empirical life test data.
Application of life models can be used to optimize design
(offline) and maximize asset utilization (online).
NREL is pursuing battery life models with physics-based
descriptions of degradation mechanisms that could both
reduce time-to-market and advise longer-life cell designs.
NATIONAL RENEWABLE ENERGY LABORATORY
Acknowledgments
23
DOE Vehicle Technologies
Brian Cunningham
David Howell
US Army/TARDEC
Yi Ding
DOE ARPA-E
Ilan Gur
NASA Jet Propulsion Laboratory Marshall Smart
Idaho National Laboratory Kevin Gering
HRL Labs John Wang, Ping Liu
Universit de Picardie Jules Verne Charles Delacourt
Boeing John C. Hall
S. California Edison Naum Pinsky, Loic Gaillac