Intrinsic degradation variability in commercial lithium

A01: Joint General Session: Batteries and Energy Storage -and- Fuel Cells, Electrolytes, and Energy Conversion
Abstract #A01-0129, Battery System IV, Thursday October 15 2015
Intrinsic degradation variability in commercial
lithium-ion batteries
Arnaud Devie
arnaud.devie@hawaii.edu
Matthieu Dubarry, Patrice Cabanel, Bor Yann Liaw
1680 East West Road, POST 109, Honolulu, HI 96822
Ph: (808) 956-2349  Fax: (808) 956-2336
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Assessing Cell-to-cell Variations
• HNEI’s know-how
50 LG 18650 cells
2800mAh, 4.3V
GIC | LCO-NMC blend
Dubarry et al., International Journal of Energy Research, 34, p216 (2010)
M. Dubarry, C. Truchot, M. Cugnet, B.Y. Liaw, K. Gering, S. Sazhin, D. Jamison, , J. Power Sources, 196, p.10328 (2011)
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Sources Of Variability In Battery
Manufacturing
Mixing
•
•
•
Composition
Morphology
Impurities
•
•
•
Duration
Environment
Calendering
Loading (g/m2)
Homogeneity
Edges
•
•
Grading
Shipping
•
•
Coating
•
Tolerances
Thickness
Porosity
Drying
•
Formation
•
•
Device
Calibration
Contact
Resistance
Residual
Moisture
Slittering
•
Filling
•
•
•
Volume
Composition
H2O ppm
Graphics from Siemens. http://www.industry.siemens.com/topics/global/en/battery-manufacturing/process/
Length
Assembly
•
•
•
Ratio
Overlay
Weld Quality
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This Experiment
Minimization of
initial differences
Matched cells
Neutralization of
extrinsic factors
Controlled environment
Long-term continuous
cycle aging
6 months
1000 cycles
[3.0 4.3]V
-1.5C DIS | C/2 CH
Evolution of the cell-tocell variations ?
Calibration across channels
5
Metric 1: Resistance
Ohmic resistance (R)
=
𝑅=
𝑑𝑉
𝑑𝐼
Outliers
Upper Extreme
50% of the population
Ohmic resistance
rose
Upper Quartile
ca. 50% over 1000 cycles
Stable statistical dispersion
Median
Lower Quartile
Whisker
Lower Extreme
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Metric 2: Kinetics
Rate Capability (rC)
Q𝐶
𝒓𝑪 =
σ = 1.1%
5x
σ = 5.6%
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𝑸𝑪 𝟏
𝑸𝑪 𝟓
Q𝐶
1
Q
Significant degradation of
the rate capability
Statistical dispersion rose
5X!
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Metric 3: Thermodynamic Capacity
Capacity ration (Qr)
𝑸𝒓 =
𝒅𝑸
𝒅𝑺𝑶𝑪
OCV
5x
DIS
100
0
dQ
dSOC
Capacity ration decreased
regularly
Statistical dispersion rose
5X!
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OCV Curves
1000 cycles
Initial
Changes in the OCV curve
=> Thermodynamic balance modified
4%
M. Dubarry, V. Svoboda, R. Hwu, and B. Y. Liaw, J. Power Sources, 174, p.1121 (2007)
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Thermodynamic balance
and degradation modes
Variation in
thermodynamic
balance
=
f(LAMPE,
LAMNE,
LLI)
LAMPE
LLI
LAMNE
M. Dubarry, C. Truchot, and B. Y. Liaw, J. Power Sources, 219, p.204 (2012)
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Incremental Capacity Analysis
dQ/dV
Switch to
dQ/dV
LLI
LAMNE
A more
intuitive
representation
LAMPE
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Loss of Active Material (LAM)
LAMPE
LAMNE
QPE ∝
Stable Positive Electrode Capacity
LAMPE is not detectable (ca. 0%)
Li0.5C6
Li0C6
Stable Negative Electrode Capacity
LAMNE is not detectable (ca. 0%)
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Loss of Lithium Inventory (LLI)
LLI
Exp. dQ/dV
Results of ‘alawa emulation
Experimental dQ/dV consistent
with up to 25% LLI
http://www.soest.hawaii.edu/HNEI/alawa/
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Loss of Lithium Inventory (LLI)
‘alawa toolbox
Comparison of emulated and
experimental dQ/dV after 1000
cycles with LLI as the degradation
mode
LLI
Gradual increase of LLI
Statistical dispersion rose
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Conclusion
Many sources of variability in the manufacturing of lithium-ion cells
Tight control over the cell-to-cell variations can be achieved at the end of the
assembly line
Grading & Matching
But, it is not sufficient to achieve tight control over the cycle life of these cells
Capacities & Kinetics diverged
We uncovered a possible thermodynamic origin to this variability
Main driver: spread in susceptibility to Loss of Lithium Inventory (LLI)
Δ
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Acknowledgement
Funding:
Idaho National Laboratory
US DOE EERE ABR
(Contract No. DE-AC07-05ID14517).
Mahalo for your attention! Questions ?
Contact:
arnaud.devie@hawaii.edu
matthieu.dubarry@gmail.com
boryann.liaw@gmail.com
Full publication list available on
http://www.soest.hawaii.edu/HNEI/alawa/
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