# Accelerated rate calorimetry dedicated to the modelling of Li-ion batteries thermal runaway of fresh and aged cells

Sara Abada, Martin Petit, Amandine Lecocq, Guy Marlair, Valérie

Sauvant-Moynot, François Huet

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Sara Abada, Martin Petit, Amandine Lecocq, Guy Marlair, Valérie Sauvant-Moynot, et al. Accelerated rate calorimetry dedicated to the modelling of Li-ion batteries thermal runaway of fresh and aged cells. 48ème édition des Journées de Calorimétrie et d'Analyse Thermique (JCAT48), May 2017, Rueil-Malmaison, France. hal-04017372

HAL Id: hal-04017372

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Submitted on 14 Mar 2023

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Distributed under a Creative Commons Attribution 4.0 International License
# Accelerated rate calorimetry dedicated to the modelling of Li-ion batteries thermal runaway of fresh and aged cells

Sara Abada¹, Martin Petit¹*, Amandine Lecocq², Guy Marlair², Valérie Sauvant-Moynot¹, François Huet³

¹IFP Energies Nouvelles, Rond-Point de l'échangeur de Solaize, BP 3 - 69360 Solaize, France *sara,abada@ifpen,fr

²INERIS Parc Technologique ALATA - BP 2 60550 Verneuil-en-Halatte, France

³UMR8235 - LISE; CNRS; UPMC Univ Paris 06, F-75005 Paris, France

<figure><img src="image_2.png" /><figcaption>Tesla Model S,
USA, 2013</figcaption></figure>

<figure><img src="image_3.png" /><figcaption>Boeing 787 Dreamliner
Japan Airlines, 2013</figcaption></figure>

<figure><img src="image_4.png" /><figcaption>Cycling site,
UK, 2008</figcaption></figure>

## CONTEXT & GOAL

* Li-ion rechargeable batteries are currently the preferred solution to store electrical energy.

* Many incidents on different applications are related to battery safety.

* The thermal runaway has been identified as a major safety concern with Li-ion batteries on their full value chain¹.

<figure><img src="image_5.png" /></figure>

<figure><img src="image_6.png" /><figcaption>Prada et al, VPPC 2010</figcaption></figure>

<figure><img src="image_7.png" /></figure>

Develop and validate physical and 3D model of Li-ion battery electro-thermal behavior nearby thermal runaway conditions, for a better understanding of phenomena as basis for improved engineering.

## COUPLED MODELING/EXPERIMENTAL APPROACH

### Experiments

* Choice of 3 relevant technologies

* 2 LFP/C cells

* 1 NMC/C cell

<figure><img src="image_8.png" /><figcaption>A123 2,3 Ah</figcaption></figure>

<figure><img src="image_9.png" /><figcaption>LifeBatt 15 Ah</figcaption></figure>

<figure><img src="image_10.png" /><figcaption>PurePower HE 30 Ah</figcaption></figure>

* Calendar aging of cells

* Accelerated aging

* @ high State of Charge (SOC): 100%

* @ high Temperature : 60 ° C

* In order to reach 2 aging targets:

* 10 % of capacity loss

* 30% of capacity losses

* Abusive tests

* Heat-Wait and Search on Battery Testing Calorimeter (BTC) device for model calibration and validation

<figure><img src="image_11.png" /></figure>

<figure><img src="image_12.png" /></figure>

<figure><img src="image_13.png" /></figure>

<figure><img src="image_14.png" /></figure>

### Modeling

* Coupling of 3 submodels

* 3D thermal model

* Static aging submodel

* Taking into account the formation of a SEI layer on the negative electrode

* 0D cell chemical degradation model

* Based on the four main degradation mechanisms

<figure><img src="image_15.png" /></figure>

## RESULTS

* Evidence of 3 key temperatures on BTC tests for all cells:

* T₁: First exothermal reaction / end of safe phase

* T₂: Fusion of the separator

* T₃: Thermal runaway

■ Stade3"Accelerating TR"

■ Stade2"Self heating"

■ Stade1"Safe"

<figure><img src="image_16.png" /></figure>

<figure><img src="image_17.png" /></figure>

* Using of modeling to further discuss the experiments:

* First exothermal reaction postponed in aged cells

* Passivation effect of the SEI layer formed during aging

* The second degradation reaction is slower

<figure><img src="image_18.png" /></figure>

Fresh A123s cell

Aged A123s cell
(30% capacity fade)

## CONCLUSIONS AND PERSPECTIVES

* An original experimental/modeling approach was developed to understand the effect of aging on Li-ion batteries safety

* the coupled thermal runaway model was validated at the cell level on BTC tests at INERIS testing plateform

* the validated model was used in order to discuss why aged cells appear safer than fresh ones

* Further work has to be done to take into account cycling aging:

* Study of safety degradation linked to cycling aging (Li plating...)

* Study of high energy cells with up-to-date Li-ion technologies

[1] S. Abada et al., "Safety focused modeling of lithium-ion batteries: A review," J. Power Sources, vol. 306, pp. 178-192, 2016.