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  • 1
    Online Resource
    Online Resource
    The Electrochemical Society ; 2022
    In:  ECS Meeting Abstracts Vol. MA2022-02, No. 3 ( 2022-10-09), p. 222-222
    In: ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2022-02, No. 3 ( 2022-10-09), p. 222-222
    Abstract: State-of-the-art Li-ion cells can have decades of lifetime ( 〉 40 years) and tremendous cycle life greater than 10000 cycles 1 . Such incredible cells greatly exceed the goal of 80% capacity retention after 800 cycles, promoted by some as sufficient for electric vehicles (EVs). However, by 2030 it is projected that more than 90% of all Li-ion batteries will be used to power vehicles 2 , with very few remaining for energy storage from intermittent renewables which must displace fossil fuels for power generation. The batteries in electric vehicles will represent a vast amount of energy storage capacity, which can be harnessed using vehicle to grid (V2G) technology. Batteries with that can maintain 80% of their capacity after a mere 800 cycles are unsustainable since most of the charge-discharge cycles in V2G will occur when the EV is stationary. For this reason, ultra-long-lived cells are a critical component of a sustainable future. In this talk, we will discuss the important role of graphite material and upper cut-off voltage (UCV) on the lifetime of NMC811 cells, and how avoiding volume contraction in Ni-rich materials yields cells that should be eminently suitable V2G applications 3,4 . Additionally, we will discuss the results of a two-year study on the impact of C-rate, depth of discharge (DoD), UCV, and temperature on the lifetime of NMC811 cells. Finally, we will demonstrate that NMC cells with a low UCV, with an emphasis on Ni-rich materials, yield greater energy throughput compared to their higher energy counterparts due to their prolonged lifetime. The $/kWh metric is surely important when selecting a battery technology, but the levelized cost of energy over the battery lifetime is more important when batteries last for many decades. References Harlow, J. E. et al. A Wide Range of Testing Results on an Excellent Lithium-Ion Cell Chemistry to be used as Benchmarks for New Battery Technologies. Journal of The Electrochemical Society 166 , A3031–A3044 (2019). Pillot, C. The Rechargeable Battery Market and Main Trends 2018-2030 . https://rechargebatteries.org/wp-content/uploads/2019/02/Keynote_2_AVICENNE_Christophe-Pillot.pdf (2019). Eldesoky, A. et al. Impact of Graphite Materials on the Lifetime of NMC811/Graphite Pouch Cells: Part I. Material Properties, ARC Safety Tests, Gas Generation, and Room Temperature Cycling. Journal of The Electrochemical Society 168 , 110543 (2021). Eldesoky, A. et al. Impact of Graphite Materials on the Lifetime of NMC811/Graphite Pouch Cells: Part II. Long-Term Cycling, Stack Pressure Growth, Isothermal Microcalorimetry, and Lifetime Projection. Journal of The Electrochemical Society 169 , 010501 (2022).
    Type of Medium: Online Resource
    ISSN: 2151-2043
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2022
    detail.hit.zdb_id: 2438749-6
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  • 2
    Online Resource
    Online Resource
    The Electrochemical Society ; 2020
    In:  ECS Meeting Abstracts Vol. MA2020-02, No. 4 ( 2020-11-23), p. 666-666
    In: ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2020-02, No. 4 ( 2020-11-23), p. 666-666
    Abstract: State-of-the-art Li-ion batteries (LIBs) typically consist of a graphite anode with a capacity of 372 mAh g -1 and a cathode material consisting of a layered transition metal oxide in the form of LiMO 2 , where M = Ni, Mn, Co or Al (NMC and NCA material), or olivine-type material in the form of LMPO 4 , where M = Fe, such as LiFePO 4 (LFP). Proposed degradation mechanisms for the cathode material in LIBs include transition metal dissolution (TMD), particle cracking and phase transformation, which are believed to contribute to significant capacity fade due to the loss of cathode active material 1 . Here, we report the use of scanning Micro X-Ray Fluorescence (µXRF) to investigate the effects of cell drying conditions and VC additive on the extent of TMD in LFP type cells and its subsequent deposition on the anode surface. For quantitative analysis, we prepared a calibration wedge made up of a pristine graphite anode with a known linear gradient of sputtered Fe. Figure 1a shows the µXRF images of the calibration sample and blank, from which we were able to correlate known TM concentrations to an observed signal intensity in the form of net count per area to facilitate accurate quantification, schematically shown in Fig. 1b . Unlike previous reports of XRF use in TMD analysis 2 , our approach allows us to quantify TM concentration deposited on our anodes without having to alter the surface by DMC washing, or through ball-milling, which preserves the nature of the sample and allows us to extract both quantitative and qualitative information (such as element distribution) from our aged cells using matrix-matched calibrants. In this work, we demonstrate how our scanning µXRF approach enabled us to visualize the distribution of TMs and other elements present on the anode surface and quantify TMD in LFP Li-ion cells. We show that Fe dissolution can be greatly reduced with rigorous cell drying and appropriate choice of additives. Additionally, we report the presence of locally high TM concentration spots on the anode which we believe are due to non-uniformities in cell stack pressure. Finally, we observe that the extent of TMD is normally not significant enough to be responsible for cell capacity fade due to active material loss, and propose how Fe dissolution might be contributing to a more complicated cell failure mechanism which will be important to investigate in future work to understand its impact on cycle life. References: Börner, M. et al. Degradation effects on the surface of commercial LiNi0.5Co0.2Mn0.3O2 electrodes. J. Power Sources 335 , 45–55 (2016). Evertz, M., Lürenbaum, C., Vortmann, B., Winter, M. & Nowak, S. Development of a method for direct elemental analysis of lithium ion battery degradation products by means of total reflection X-ray fluorescence. Spectrochim. Acta - Part B At. Spectrosc. 112 , 34–39 (2015). Figure 1
    Type of Medium: Online Resource
    ISSN: 2151-2043
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2020
    detail.hit.zdb_id: 2438749-6
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  • 3
    Online Resource
    Online Resource
    The Electrochemical Society ; 2019
    In:  ECS Meeting Abstracts Vol. MA2019-04, No. 1 ( 2019-06-30), p. 2-2
    In: ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2019-04, No. 1 ( 2019-06-30), p. 2-2
    Abstract: As the adoption of electric vehicles continues to increase, there is a growing demand for faster charging lithium-ion cells to compete with the convenience of fuel-powered vehicles. Yet even for modern designs, rapidly charging lithium-ion cells can cause a decrease in cycle and calendar lifetimes. This is largely attributable to the large overpotentials required to apply large currents, which can lead to unwanted lithium metal plating at the graphite electrode surface. Moreover, as electrode thickness increases for higher energy density cells, lithium-ion transport in the electrolyte becomes limited, leading to even larger overpotentials. This work will present novel electrolytes with improved lithium-ion transport properties. Several co-solvent systems were identified based on the viscosity, permittivity (dielectric constant), and DFT-calculated electrochemical stability windows of the pure compounds. Several formate, nitrile, ketone, and amide co-solvents will be shown to increase the ionic conductivity of LiPF 6 in conventional organic-carbonate-based solutions (Figure 1). Based on gas production during the first formation cycle in Li[Ni 1-x-y Co x Al y ]) 2 /graphite-SiO pouch cells, five candidates were identified: methyl formate (MF), ethyl formate (EF), propionitrile (PN), isobutyronitrile (iBN), and dimethyl formamide (DMF). High temperature storage (60°C), ultrahigh-precision coulometry (UHPC), and long-term cycling results will be presented showing that MF offers the greatest balance between conductivity increase and cell lifetime. PN may prove useful for low temperature ( 〈 40°C) applications. Figure 1 – a) Ionic conductivity of 1.2 mol L −1 LiPF 6 solutions prepared with 20% of co-solvent and 80% of a 25:5:70 mixture by weight of ethylene carbonate, ethyl methyl carbonate, and dimethyl carbonate, respectively. b) Solution conductivities relative to control solution, i.e., no co-solvent. Co-solvents include isobutyl acetate (iBA), methyl propionate (MP), methyl butyrate (MB), methyl formate (MF), ethyl formate (EF), n-propyl formate (nPF), isobutyl formate (iBF), propionitrile (PN), isobutyl nitrile (iBN), methyl ethyl ketone (MEK), and dimethyl formamide (DMF). Figure 1
    Type of Medium: Online Resource
    ISSN: 2151-2043
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2019
    detail.hit.zdb_id: 2438749-6
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  • 4
    Online Resource
    Online Resource
    Elsevier BV ; 2011
    In:  Water Research Vol. 45, No. 18 ( 2011-11), p. 6173-6180
    In: Water Research, Elsevier BV, Vol. 45, No. 18 ( 2011-11), p. 6173-6180
    Type of Medium: Online Resource
    ISSN: 0043-1354
    Language: English
    Publisher: Elsevier BV
    Publication Date: 2011
    detail.hit.zdb_id: 202613-2
    detail.hit.zdb_id: 1501098-3
    SSG: 14
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  • 5
    In: ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2022-01, No. 2 ( 2022-07-07), p. 200-200
    Abstract: 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 60 o C is around 500 hours with a base electrolyte of 1.5 M LiPF 6 (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/cm 2 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 LiPF 6 , LiFSI (Lithium bis(fluorosulfonyl)imide) and LiPF 6 +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 LiPF 6 EC:DMC 3:7 and b) 1.5 M LiPF 6 +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
    Type of Medium: Online Resource
    ISSN: 2151-2043
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2022
    detail.hit.zdb_id: 2438749-6
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  • 6
    Online Resource
    Online Resource
    The Electrochemical Society ; 2021
    In:  ECS Meeting Abstracts Vol. MA2021-02, No. 5 ( 2021-10-19), p. 1893-1893
    In: ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2021-02, No. 5 ( 2021-10-19), p. 1893-1893
    Type of Medium: Online Resource
    ISSN: 2151-2043
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2021
    detail.hit.zdb_id: 2438749-6
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  • 7
    In: Electrochimica Acta, Elsevier BV, Vol. 53, No. 2 ( 2007-12), p. 688-694
    Type of Medium: Online Resource
    ISSN: 0013-4686
    Language: English
    Publisher: Elsevier BV
    Publication Date: 2007
    detail.hit.zdb_id: 1483548-4
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  • 8
    In: ECS Transactions, The Electrochemical Society, Vol. 3, No. 1 ( 2006-10-20), p. 241-248
    Abstract: Vacuum deposition techniques were used to prepare composition spread samples of thin film Fe-C-N catalysts. After deposition, catalyst films were thermally treated to induce structural and composition changes. Catalytic activity was found to be at its largest when the films were annealed at ca. 800{degree sign}C. At this temperature, partial graphitization of the film occurred but it still contained a significant amount of nitrogen, which is required to have an active site. Above 800{degree sign}C, a significant quantity of Fe3C, which is inactive and not stable in acid, was formed. Single composition thin films were also prepared, thermally treated, and tested in a 50-cm2 fuel cell. After thermal treatment of the catalyst, the fuel cell performance was significantly improved.
    Type of Medium: Online Resource
    ISSN: 1938-5862 , 1938-6737
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2006
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  • 9
    In: ECS Transactions, The Electrochemical Society, Vol. 33, No. 1 ( 2010-10-01), p. 143-152
    Abstract: Nanostructured thin film catalysts (NSTF) with widely varying compositions of PtxMyNz (M, N = Ni, Co, Zr, Hf, Fe, Mn) have been evaluated for 0 〈 x,y,z 〈 1. The catalysts' activity for oxygen reduction (ORR) was measured in 50 cm2 fuel cell membrane electrode assemblies. PtxNiy was found to be unique in showing an extraordinarily sharp peak in ORR activity as a function of the as-made composition around x=3, y=7. This composition gave a corresponding fcc lattice parameter of 3.71 Angstroms and a grain size of 7.5 nm. Both surface area and specific activity increases contribute to the increased mass activity. The ORR mass activity of the Pt3Ni7 is 60% higher than for the NSTF standard Pt68Co29Mn3 alloy.
    Type of Medium: Online Resource
    ISSN: 1938-5862 , 1938-6737
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2010
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  • 10
    Online Resource
    Online Resource
    American Chemical Society (ACS) ; 2016
    In:  Chemistry of Materials Vol. 28, No. 7 ( 2016-04-12), p. 2461-2461
    In: Chemistry of Materials, American Chemical Society (ACS), Vol. 28, No. 7 ( 2016-04-12), p. 2461-2461
    Type of Medium: Online Resource
    ISSN: 0897-4756 , 1520-5002
    Language: English
    Publisher: American Chemical Society (ACS)
    Publication Date: 2016
    detail.hit.zdb_id: 1500399-1
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