Impact of Functionalization and Co-Additives on Dioxazolone Electrolyte Additives

Gauthier, Roby; Hall, David S.; Lin, Katherine; Baltazar, Jazmin; Hynes, Toren; Dahn, J. R.

doi:10.1149/1945-7111/ab8ed6

Cited by 8 publications

(6 citation statements)

References 69 publications

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“…8 was thus calculated using the lowest Gibbs free energy configurations of both LiDFDOP and Li 2 DFDOP and thus determined to be 2.14 V vs Li/Li + . The full cell voltages corresponding to this standard reduction potential are 1.51 V for SC NMC532/AG cells and 1.46 V for BM NMC811/ AG cells using a method previously described, 47,48 very close to the experimental values of 1.55 V for SC NMC532/AG and 1.50 V for BM NMC811/AG cells, derived from the onset of the reduction feature in the dQ/dV graph of Figs. 6d-6e.…”

Section: Resultssupporting

confidence: 74%

Lithium Difluoro(dioxalato) Phosphate as an Electrolyte Additive for NMC811/Graphite Li-ion Pouch Cells

Song

Gauthier²,

Taskovic³

et al. 2022

J. Electrochem. Soc.

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Lithium difluoro(dioxalato)phosphate (LiDFDOP) has been systemically studied as an electrolyte additive singly and in combination with co-additives in LiNi0.8Mn0.1Co0.1O2 (NMC811)/artificial graphite (AG) pouch cells. Long-term cycling tests at room and elevated temperatures (20°C, 40°C, and 55°C) with different upper cutoff voltages (4.06 and 4.20 V) were performed. These results were combined with ultra-high precision coulometry, ex-situ gas measurements, and automatic cell storage tests to reveal multiple aspects of cell performance. A density functional theory calculation has also been performed and compared to formation data to reveal the mechanistic aspects of LiDFDOP reduction. Radar plots and a figure-of-merit approach were further utilized to summarize results and rank additive and additive combination performance for the NMC811/AG cells. This work highlights an effective additive and suitable co-additives for use in NMC811/graphite cells and gives important insights for future electrolyte additive studies.

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Section: Resultssupporting

confidence: 74%

Lithium Difluoro(dioxalato) Phosphate as an Electrolyte Additive for NMC811/Graphite Li-ion Pouch Cells

Song

Gauthier²,

Taskovic³

et al. 2022

J. Electrochem. Soc.

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“…The presence of the rollover cell failure can be also demonstrated in commercial pouch bag cells, which are regularly used for highly reproducible electrolyte research studies. , As shown in Figure a, for NCM∥graphite pouch cells with varied cathode active materials, i.e. , C-NCM523 and LiNi 1/3 Co 1/3 Mn 1/3 O 2 (NCM111), they both suffer from rollover failure at different stages, which is highly reproducible.…”

Section: Resultsmentioning

confidence: 87%

Demonstrating Apparently Inconspicuous but Sensitive Impacts on the Rollover Failure of Lithium-Ion Batteries at a High Voltage

Klein

Bärmann

Stolz

et al. 2021

ACS Appl. Mater. Interfaces

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Layered oxides, such as Li[Ni0.5Co0.2Mn0.3]O2 (NCM523), are promising cathode materials for operation at a high voltage, i.e., high-energy lithium-ion batteries. The instability-reasoned transition metal dissolution remains a major challenge, which initiates electrode cross-talk, alteration of the solid electrolyte interphase, and enhanced Li-metal dendrite formation at the graphite anode, consequently leading to rollover failure. In this work, relevant impacts on this failure mechanism are highlighted. For example, a conventional coating of NCM523 with aluminum oxide as a typical high-voltage modification improves kinetic aspects but can only postpone the rollover failure to later charge/discharge cycles. Interestingly, a similar effect on the rollover failure is observed merely after modification of the cell formation protocol, i.e., the first cycles. Further influences of specific test protocols are highlighted and show that the rollover failure even disappears at C-rates above 2C, which can be attributed to a more homogeneous distribution of Li-metal dendrite formation. It is worth noting that a variation of anode porosity can reveal similar effects, as, e.g., variations in anode processing also impact Li dendrite distribution and the appearance of rollover failure. Overall, the rollover failure is a valid but complex phenomenon, which sensitively depends on apparently inconspicuous parameters and should not be disregarded.

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“…Pouch cells were cycled to an UCV of 4.4 V at a current corresponding to C/3 using the voltage-hold protocol at 40 °C. It is evident from previous studies 6,7,38 by our group that using corresponding co-additives may provide complementary effects to provide adequate passivation on the surfaces of both electrodes. This was shown by Ma et al who studied the additive LFO in combination with other passivating additives, such as FEC, VC, or DiFEC.…”

Section: Resultsmentioning

confidence: 97%

Performance of a Novel In-Situ Converted Additive for High Voltage Li-ion Pouch Cells

Azam

Meisner

Aiken

et al. 2022

J. Electrochem. Soc.

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In search of new classes of additives for high-voltage NMC/graphite lithium-ion cells, the precursor additive bis(trimethylsilyl) malonate (bTMSM) is shown to be activated via a spontaneous reaction with LiPF6 and LiBF4 salts in carbonate-based electrolyte to form lithium tetrafluoro(malonato)phosphate (LiTFMP), and lithium difluoro(malonato)borate (LiDFMB), respectively. The reaction schemes and rates were studied via nuclear magnetic resonance spectroscopy and gas chromatograph mass spectrometry. The effects of LiTFMP and LiDFMB on high-voltage electrochemical performance were then examined up to 4.5 V in Li[Ni0.4Mn0.4Co0.16]O2 (NMC442)/graphite and Li[Ni0.6Mn0.4Co0.0]O2 (NMC/640)/graphite pouch cells using aggressive voltage-hold cycling, long-term charge/discharge cycling, storage experiments, electrochemical impedance spectroscopy, and gas evolution measurements. While in-situ converted additives suffer from gassing issues due to the presence of trimethylfluorosilane gas, a side product of the in-situ reaction of bTMSM with LiPF6, the cycling and storage capability for the activated additives under study shows competitive performance and controlled impedance when compared to other well-known high voltage additives. Micro x-ray fluorescence spectroscopy confirmed that LiTFMP successfully minimizes the rate of transition metal deposition on the surface of graphite apparently by forming a protective agent at the cathode surface, hence allowing for improved cycling performance at high voltages.

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Impact of Functionalization and Co-Additives on Dioxazolone Electrolyte Additives

Cited by 8 publications

References 69 publications

Lithium Difluoro(dioxalato) Phosphate as an Electrolyte Additive for NMC811/Graphite Li-ion Pouch Cells

Lithium Difluoro(dioxalato) Phosphate as an Electrolyte Additive for NMC811/Graphite Li-ion Pouch Cells

Demonstrating Apparently Inconspicuous but Sensitive Impacts on the Rollover Failure of Lithium-Ion Batteries at a High Voltage

Performance of a Novel In-Situ Converted Additive for High Voltage Li-ion Pouch Cells

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