锂电老化机理和诊断分析全英文.pdf
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1、www.inl.gov Diagnostic Testing and Analysis Toward Understanding Aging Mechanisms and Related Path Dependence Kevin L. Gering, PhD Energy Storage complemented by Equivalent Circuit Models (ECMs). INL Essential Modeling Tools Key Elements are Patent Pending Life Data +Mech. Models =Early Diagnosis an
2、d Predictive Analyses Cell 80 Cell 14 Time, weeks 020406080100120140160 Conductance Fade, % 0 10 20 30 40 50 60 70 Data with 0.005 Ohm offset Data with No offset IR Ohmic drop, EIS data Legend: A: IR Ohmic term B: SEI, chem/electronic C: SEI, phys/structure D: Rct,o (intrinsic) Total Net SEI Contrib
3、ution (B+C) A B D C Modeling Cell Conductance Results from two-model synergy (MSM + -BV Kinetics) Key insights into cell operation and rate-based mathematics allows accurate modeling and high-fidelity diagnostic analysis of conductance behavior in electrochemical cells. Cell conductance has a princi
4、pal influence on attainable power, decreasing over the life of a cell. Based on data for EIS semicircle RHS edge, Gen2 cells cycle-life tested at 25 C. INL Kinetics Modeling Based on an improved form of Butler-Volmer expression that is well-suited for Li-ion systems. Model gives extremely accurate p
5、redictions over (T, I, tpulse , cell aging) when coupled with an advanced set of rate expressions. Current, A 0.0010.010.1110 Total Resistance, Ohm 0.0 0.5 1.0 1.5 2.0 2.5 3.0 after 1 second 2 seconds 3 seconds 4 seconds 5 seconds 6 seconds 7 seconds 8 seconds 9 seconds 10 seconds 0.5 second 0.5 s 1
6、0 s Solid Curves: Model Predictions Cell 80 (20% Power Fade) Rtotalat 30 oC along pulse timeline Approximate trend line for io Current, A 0.0010.010.1110 Total Resistance, Ohm 0.0 0.5 1.0 1.5 2.0 2.5 3.0 after 1 second 2 seconds 3 seconds 4 seconds 5 seconds 6 seconds 7 seconds 8 seconds 9 seconds 1
7、0 seconds 0.5 second 0.5 s 10 s Solid Curves: Model Predictions Cell 80 (20% Power Fade) Rtotalat 30 oC along pulse timeline Approximate trend line for io Cell 80 (20% Power Fade) Rtotalat 30 oC along pulse timeline Approximate trend line for io Current, A 0.0010.010.1110 Total Resistance, Ohm 0.01
8、0.1 1 10 oC -40 -30 -20 -10 0 20 30 10 Symbols: Test Data Solid Curves: Model Rtotalat 10 s over temperature Current, A 0.0010.010.1110 Total Resistance, Ohm 0.01 0.1 1 10 oC -40 -30 -20 -10 0 20 30 10 Symbols: Test Data Solid Curves: Model Rtotalat 10 s over temperature 0.0 0.5 1.0 1.5 2.0 2.5 3.0
9、0 2 4 6 8 0.01 0.1 1 10 Total Resistance, Ohm Time During Pulse, s Current, A Cell 80 at 30 oC 0.0 0.5 1.0 1.5 2.0 2.5 3.0 0 2 4 6 8 0.01 0.1 1 10 Total Resistance, Ohm Time During Pulse, s Current, A Cell 80 at 30 oC .and many other performance quantities. Time, Weeks 050100150200250 C1/1 Capacity
10、Fade Term, % 0 10 20 30 40 50 Data Overall Model Results Related to Li+ Related to Active Sites Offsets due to C/1 rate limitations Test data covers 140 weeks Time, Weeks 050100150200250 C1/1 Capacity Fade Term, % 0 10 20 30 40 50 Data Overall Model Results Irreversible total Irreversible, Li+ Irrev
11、ersible, Active Sites Reversible total Reversible, Li+ Reversible, Active Sites The rate of lithium consumption is high during initial time (continued SEI formation; side reactions), but tapers off considerably by 30 weeks. Reversible contributions to fade dominate at early time, are tied primarily
12、to active sites, and undergo a maximum at around 150 weeks. In comparison, irreversible losses grow steadily over the time period. Capacity fade is dominated by mechanisms that impact active sites, initially by reversible mechanisms through about 180 weeks, then by irreversible mechanisms thereafter
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