Stress analysis of lithium-based rechargeable batteries using micro and macro scale analysis

Utsav Kumar Atanu K. Metya Jayant K. Singh Department of Chemical Engineering IIT Kanpur

INTRODUCTION
Christensen and Newman, Journal of Electrochemical Society, 2006
Estimated stress generation in LiyMn2O4 and carbon electrodes separately.

Zhang et al., Journal of Electrochemical Society, 2007

Stress distribution inside one single electrode particle using numerical simulation.

Zhang et al., Journal of Electrochemical Society, 2008

Intercalation induced stress and heat generation within single Lithium-Ion battery cathode particles.

Golmon et al., Computers and Structures, 2009

Electrochemical mechanical interaction phenomena at macro, meso and micro scale.

OBJECTIVE
Study of intercalation and thermal stress generation in Li ion rechargeable battery incorporating the effect of Li ion electrode concentration on electrode diffusivity coefficient and stress generation.
Stress Analysis of Lithium-Based Rechargeable Batteries using micro and macro scale analysis 2

STRUCTURE

Source: spectrum.ieee.org Source: srinivasan et al., 2003

Stress Analysis of Lithium-Based Rechargeable Batteries using micro and macro scale analysis

Battery Electrode

Battery Electrolyte

Thermal Analysis

Stress Analysis

is = - s s ,eff f s cs Ws c = .(Ds ( cs s h )) t RT
Effect of hydrostatic stress on Li ion flux

Butler-Volmer Reaction

iloc = i0 (exp( a a F h ) - exp(

RT
Source: NREL ,National Renewable Energy Laboratory

- a cFh RT

))

h = f s - D f s ,film - f l - Eeq
i0 = F (kc ) a (ka ) c (cs ,max - cs ) a (cs ) c (cl / cl ,ref )
a a a a aa
Reference: Doyle et al., 1996; Rosas et al., 2011 and Fuel cells and Battery module, COMSOL

Stress Analysis of Lithium-Based Rechargeable Batteries using micro and macro scale analysis

Battery Electrode

Battery Electrolyte

Thermal Analysis

Stress

il = - s l ,eff f l +

2s l ,eff RT F

(1 + ln f / ln cl )(1 - t+ ) ln cl
Concentration gradient

el

cl t

+ .Nl = Rl
Reaction
il t+ F
Rl = -

Flux
Nl = - Dl ,eff cl +

av ,m

u Li + ,m iloc F

Diffusion and Migration

Source: spectrum.ieee.org

Reference: Doyle et al., 1996; Rosas et al., 2011 and Fuel cells and Battery module, COMSOL

Stress Analysis of Lithium-Based Rechargeable Batteries using micro and macro scale analysis

Battery Electrode

Battery Electrolyte

Thermal Analysis

Stress

Qrev = Qrea

Qirr = Qact + Qohm

Ui T

Qrea = av ,i iloc ,iT

Qact = av ,i iloc ,i (f s ,i - f l ,i - Ui )

Qohm
Source: Comsol Multiphysics

2RT eff k (t+ - 1)(1 + d ln f / d ln c ) F eff eff eff cl = s s f s . f s + k f l . f l + k D . f l cl k Deff =

Thermal Strain

ethermal = a T

Reference: Srinivasan and Wang, 2003; Kumaresan et al., 2008 and Fuel cells and Battery module, COMSOL

Stress Analysis of Lithium-Based Rechargeable Batteries using micro and macro scale analysis

Battery Electrode

Battery Electrolyte

Thermal Analysis

Stress

cs t

= .(Ds ( cs -

Ws c RT

s h ))

s h = (s r + 2s t ) / 3

Effect of hydrostatic stress on Li ion flux

J = - Mcs m

m = m0 + RT ln X - W h s

er =
et =

1 W (s r - 2J s t ) + % c E 3
1 W [(s t - J (s r + s t )] + % c E 3
Source: intechopen.com r0 r0 r r 2 2 2 t 3 3 3 3 0 0 0 0 0 0 Reference: Zhang et al., 2007; Zhang et al., 2008 and Xiao et al., 2010

sr =

2W E 1 ( 3(1 - J ) r

% dr - 1 % dr ) cr cr r

s =

W E 2 ( 3(1 - J ) r

% dr - 1 % 2dr - % c) cr cr r
7

Stress Analysis of Lithium-Based Rechargeable Batteries using micro and macro scale analysis

MODELING
Butler Volmer
Cl, J Cs J

Electrode Solids State Diffusion

Cs

Electrode & Electrolyte Species/Charge Transport

T

Stress Intercalation and Thermal

T

, i

Thermal Heat Generation/ Transport

Stress Analysis of Lithium-Based Rechargeable Batteries using micro and macro scale analysis

MODELING
Butler Volmer
Cl, J Cs J

Electrode Solids State Diffusion

Cs

Electrode & Electrolyte Species/Charge Transport

T

Stress Intercalation and Thermal

T

, i

Thermal Heat Generation/ Transport

Stress Analysis of Lithium-Based Rechargeable Batteries using micro and macro scale analysis

Ds as a function of Cs?
Butler Volmer
Cl, J Cs J

Ds (T)
Electrode Solids State Diffusion
Cs

Ds (Cs ,T)

Electrode & Electrolyte Species/Charge Transport

T

Stress Intercalation and Thermal

T

, i

Thermal Heat Generation/ Transport

Stress Analysis of Lithium-Based Rechargeable Batteries using micro and macro scale analysis

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LixC6 Electrode phase diffusion value (MD Simulation)

INTERACTION PARAMETERS
Graphene Layers Li-Li interaction Graphene-Li interaction AIREBO (Adaptive Intermolecular Reactive Empirical Bond-Order)
Stuart et. al, Journal of Chemical Physics, 2000

Field Parameter for Intermolecular and Columbic interactions.

Wander and Shuford, Journal of Chemical Physics, 2011

Lorentz-Berthelot combining rules

DIFFUSIVITY CALCULATION
Einstein relation - diffusion coefficient is related to the slope of the mean square displacement (MSD) of the particles over time.
2 1 d D = lim r i (t + t0 )- ri (t0 ) 6 t dt

Stress Analysis of Lithium-Based Rechargeable Batteries using micro and macro scale analysis

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DIFFUSIVITY

Similarly for LiMn2O4 Wakhira et al., Ionic State Solids, 1996 and Srinivasan et al., Journal of The Electrochemical Society, 2003 gives us the same kind of expression
Stress Analysis of Lithium-Based Rechargeable Batteries using micro and macro scale analysis

E = 81.5 meV DE D (Cs ,T ) = D298K (x )exp R (1/ T - 1/ Tref )

12

COMSOL MODEL
Anode Separator Cathode 1D electrochemical finite element model (FEM) Charge Conservation Chemical Kinetics Mass Transport (except for electrode particles) Heat Transport Fuel cell and battery module Heat Transfer module

r=12.5m

r=8.5m

2D electrode particle FEM model Li ion concentration in electrode particle Intercalation and Thermal Stress PDE module
13

Cathode Anode

Parameter Reference: Doyle et al, 1996; Srinivasan et al, 2003 and Zhang et al, 2007

Stress Analysis of Lithium-Based Rechargeable Batteries using micro and macro scale analysis

APPLIED CURRENT
ANODE SEPARATOR CATHODE

Source: srinivasan et al., 2003

Current density of 17.5 A/m2 applied Charge cycle of 1600s with 800s of discharging and charging Total number of cycles - 10 Anode kept at constant potential
Stress Analysis of Lithium-Based Rechargeable Batteries using micro and macro scale analysis 14

Electrode

Stress Analysis of Lithium-Based Rechargeable Batteries using micro and macro scale analysis

15

Electrolyte

Stress Analysis of Lithium-Based Rechargeable Batteries using micro and macro scale analysis

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Cs variation
Discharging (200s-600s) Charging (1100s-1500s)

Stress Analysis of Lithium-Based Rechargeable Batteries using micro and macro scale analysis

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AVERAGE TEMPERATURE

T (K)

t (s)

Qtotal is taken as heat generated inside Li ion battery and on the basis of that an average Temperature is calculated and used for further studies including thermal stress
Stress Analysis of Lithium-Based Rechargeable Batteries using micro and macro scale analysis 18

INTERCALATION STRESS
Anode Tangential Stress Cathode Tangential Stress

W E 2 st = ( 3 3(1 - J ) r0

% 2dr - 1 % 2dr - % cr c) cr 3 r 0 0
19

r0

Stress Analysis of Lithium-Based Rechargeable Batteries using micro and macro scale analysis

Electrode Potential

Stress Analysis of Lithium-Based Rechargeable Batteries using micro and macro scale analysis

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Normalized Stress and Potential

Stress Analysis of Lithium-Based Rechargeable Batteries using micro and macro scale analysis

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CONCLUSION
Diffusion coefficient as a function of Temperature and Li ion concentration is developed for electrodes and incorporated into model . Effect of Diffusion coefficient as a function of Li ion electrode concentration on stress value can be seen.

Tavg reaches an asymptotic value as counterbalance between heat generation and heat rejection comes to an equilibrium as time progresses.
There is an accumulation of stress with continuous use of battery, this may lead to break down of battery if it reaches the break through point limit. With continuous use of battery there is a decrease in maximum battery potential, i.e. more charge required for achieving the previous potential value as we keep on using battery.
Stress Analysis of Lithium-Based Rechargeable Batteries using micro and macro scale analysis 22

Thank You
ACKNOWLEDGEMENT
Chemical Engineering Department and DRPG, IIT Kanpur for travel support

Dr. Ramakrishnan Narayanrao, General Motors, India

Computational Nano Science Group, IIT Kanpur for their help and support

LixC6 Electrode phase diffusion value (MD Simulation)

INTERACTION PARAMETERS Graphite : AIREBO (Adaptive Intermolecular Reactive Empirical Bond-Order). Stuart et. al, Journal of Chemical Physics, 2000
1 E= 2

j i

REBO LJ E + Eij + ij

k i , j l i , j ,k

tors Ekijl .

REBO Eij = V R rij + bijV A rij

( )

( )

Li-Li interaction - Field Parameter for Intermolecular and Columbic interactions. Wander and Shuford, Journal of Chemical Physics, 2011 Graphite-Li interaction - Lorentz-Berthelot combining rules are employed for the cross interactions

Stress Analysis of Lithium-Based Rechargeable Batteries using micro and macro scale analysis

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DIFFUSIVITY CALCULATION
The diffusion coefficient can be obtained using two equivalent equilibrium methods. Einstein relation - diffusion coefficient is related to the slope of the mean square displacement (MSD) of the particles over time.
2 1 d D = lim r i (t + t0 )- ri (t0 ) 6 t dt

Green-Kubo (GK) - integration over the velocity autocorrelation function

1 D = Vi (t + t0 ) 0 (t0 ) dt V 30
Green-Kubo gives too much fluctuation as compared to Einstein relation because of low concentration of Li
Stress Analysis of Lithium-Based Rechargeable Batteries using micro and macro scale analysis 25

Lithium intercalated graphite Li0.396C6

(MD Simulation snapshot)
SIDE VIEW

INITIAL CONFIGURATION

NVT Ensemble TOP VIEW

FINAL CONFIGURATION (1ns)

Stress Analysis of Lithium-Based Rechargeable Batteries using micro and macro scale analysis

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DIFFUSIVITY at 298K
600 500 MSD (2) 400 300 200 100 0 10 20 30 Time (ps) 40 50
0 50 100 150 200

MSD (2)

Li0.208C6 Li0.396C6 Li0.500C6 Li0.604C6

1200

800

353K 298K 265K 233K

400

Time (ps)

2 1 d D = lim r i (t + t0 )- ri (t0 ) 6 t dt

(MSD)
27

Stress Analysis of Lithium-Based Rechargeable Batteries using micro and macro scale analysis

THERMAL ANALYSIS

Qirrev = Qohm + Qact

Qrev = av ,i iloc ,iT

Ui T

Stress Analysis of Lithium-Based Rechargeable Batteries using micro and macro scale analysis

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Anode-Tangential Stress Difference

Tangential Stress for Diffusivity as function of electrode Li ion and Temperature subtracted from Tangential Stress for Diffusivity as function of Temperature only vs. time
Stress Analysis of Lithium-Based Rechargeable Batteries using micro and macro scale analysis 29