Investigation of Redox Shuttle Generation in LiFePO<sub>4</sub>/Graphite and NMC811/Graphite Cells for Different Additives and Conducting Salts
Notice bibliographique
Résumé
LFP/Graphite cells are attractive because they are cheaper[1], safer[2,3] and can achieve acceptable energy density for most applications. A limitation of the LFP/Graphite cells is their inferior capacity retention at elevated temperature when compared to NMC/Graphite cells especially in the absence of electrolyte additives, e.g., VC (Vinylene carbonate), as observed by our group in a recent study[4].The time it takes for a LFP graphite cell to completely self-discharge at 60oC is around 500 hours with a base electrolyte of 1.5 M LiPF6 (Lithium hexafluorophosphate) dissolved in 7:3 DMC:EC (Dimethyl carbonate/ethylene carbonate)[4]. It also has been observed that during cycling some Fe will accumulate on the anode which can be explained by dissolution of Fe from the cathode and subsequent deposition on the anode. With the same electrolyte as mentioned before we can observe up to 0.2 μg/cm2 on the anode after 60 cycles at 40⁰C[4]. The goal of this research is to understand what is happening inside the LFP/Graphite cells by analyzing the electrolyte from cells that only did a formation procedure. We were able to extract different electrolytes from LFP/Graphite and NMC811/Graphite pouch cells. We expected the electrolyte to stay clear as it was just after preparation, but we observed yellow and red colors depending on the temperature of formation. If the electrolyte contained 2%wt VC, no color change was observed. The different electrolytes used for the experiments were LiPF6, LiFSI (Lithium bis(fluorosulfonyl)imide) and LiPF6+2%wt VC all dissolved in 7:3 DMC:EC. The extracted electrolytes were put inside coin cells with an Al foil working-electrode (WE) and a Li foil counter-electrode (CE) and cyclic voltammetry (CV) was done on them from 2.6 V - 3.75 V vs. Li+/Li. The CV traces show the presence of current in the μA range for electrolyte without VC extracted from LFP cells, indicating the presence of a reversible shuttle species. The electrolyte with no VC expected from LFP cells showed more current than the corresponding electrolyte extracted from NMC811 cells. There was almost no current in the coin cells using electrolytes with 2% VC extracted from the LFP and NMC811 cells. We also made systematic experiments at different formation temperature and different wait times before extraction. Figure 1: Observation of the different electrolytes extracted from LFP/Graphite cells with a) 1.5 M LiPF6 EC:DMC 3:7 and b) 1.5 M LiPF6 +2%wt VC EC:DMC 3:7 that did formation at 25, 40 ,55 and 70⁰C (left to right). References W. Li, Y. Cho, W. Yao, Y. Li, A. Cronk, R. Shimizu, M. A. Schroeder, Y. Fu, F. Zou, V. Battaglia, A. Manthiram, M. Zhang, and Y. S. Meng. “Enabling high areal capacity for Co-free high voltage spinel materials in next-generation Li-ion batteries”, Journal of Power Sources, 473 (2020). D. Jian, T. Xuan, D. Haifeng, Y. Ying, W. Wangyan, W. Xuezhe, and H. Yunhui. “Building Safe Lithium-Ion Batteries for Electric Vehicles: A Review”, Electrochem. Energ. Rev. 3, 1–42 (2020). W. Li, H. Wang, Y. Zhang, and M. Ouyang. “Flammability characteristics of the battery vent gas: A case of NCA and LFP lithium-ion batteries during external heating abuse”, Journal of Energy Storage, 24 (2019) E. R. Logan, H. Hebecker, A. Eldesoky, A. Luscombe, M. B. Johnson, and J. R. Dahn. “Performance and Degradation of LiFePO4/Graphite Cells: The Impact of Water Contamination and an Evaluation of Common Electrolyte Additives”, Journal of The Electrochemical Society, 167, 13 (2020) Figure 1
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Comment cette classification a été obtenuedéplier
Prédiction machine sur la base complète
Imitation des enseignantsNi prévalence calibrée, ni vérité terrain. Validation humaine à venir. Le volet Gemma est une étiquette directe du modèle pour chaque travail de la base, lue sur la notice réduite au titre. Le volet Codex est un classifieur appris des 10 348 étiquettes directes de Codex et calibré sur les taux pondérés de l'échantillon; les champs sans appui suffisant ne portent aucun appel Codex. Le mode candidate est l'union des deux volets; le consensus est leur intersection. Ces sorties portent le statut machine_predicted_unvalidated et ne sont pas des étiquettes humaines.
Scores du classifieur distillé par catégorie (deux têtes)
| Catégorie | Codex | Gemma |
|---|---|---|
| Métarecherche | 0,000 | 0,000 |
| Méta-épidémiologie (sens strict) | 0,000 | 0,000 |
| Méta-épidémiologie (sens large) | 0,000 | 0,000 |
| Bibliométrie | 0,000 | 0,000 |
| Études des sciences et des technologies | 0,000 | 0,000 |
| Communication savante | 0,000 | 0,000 |
| Science ouverte | 0,000 | 0,000 |
| Intégrité de la recherche | 0,001 | 0,000 |
| Charge utile insuffisante (le modèle a refusé de juger) | 0,001 | 0,000 |
Scores machine (provisoires)
Les deux têtes enseignantes du modèle étudiant, lues sur ce travail. Un score ordonne la base pour la relecture; il n'affirme jamais une catégorie, et le statut de validation accompagne chaque rangée tel quel.
Scores de référence d'un modèle non mature (critères de maturité non atteints, 7 itérations). Un score ordonne; il n'affirme jamais une catégorie.
score_only:v0-immature-baseline · tel quel depuis la passe de notation : score_only signifie que le nombre peut ordonner les travaux, et qu'aucune étiquette de catégorie n'en découleClassification
machine, non validéePrédiction automatique; un appel candidat d’une seule source (Gemma direct ou Codex distillé), pas un consensus.
Le détail, modèle par modèle et score par score, se trouve en fin de page sous « Comment cette classification a été obtenue ».