Operation of Li-ion batteries below −20 °C is hindered by low electrolyte conductivity and sluggish solid-state diffusion in electrodes. Li metal anodes show promise for low-temperature operation, but few electrolyte compositions exhibit high conductivity at reduced temperature while also allowing Li electrodeposition/stripping with high Coulombic efficiency. Here, we show that the Coulombic efficiency of Li metal anodes can be substantially improved at low temperatures (−60 °C) by tailoring the solid-electrolyte interphase (SEI) structure through the use of two classes of electrolyte solvents: cyclic carbonates and ethers. Cryogenic transmission electron microscopy and other methods show that fluoroethylene carbonate (FEC) induces temperature-dependent changes in the chemistry and structure of the SEI to be abundant with LiF and Li2CO3, while 17O nuclear magnetic resonance and molecular dynamics calculations show that FEC affects the solvation behavior and SEI formation process in this new electrolyte system. Our results demonstrate the promise of rechargeable Li-metal batteries to enable energy storage over a broad temperature range.

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Although Li metal batteries offer the highest possible specific energy density, practical application is plagued by Li filament growth with adverse effects on both Coulombic efficiency and battery safety. The structure and resulting properties of the solid electrolyte interphase (SEI) on Li metal is critical to controlling Li deposition morphologies and achieving high efficiency batteries. In this report, we use a combination of nuclear magnetic resonance (NMR) spectroscopy and X-ray photoelectron spectroscopy (XPS) to show that fast Li transport and low solubility at the electrode/SEI interface in 0.5 M LiNO 3 + 0.5 M LiTFSI electrolyte bi-salt in 1,3-dioxolane:dimethoxyethane (DOL:DME, 1:1, v/v) are responsible for the formation of low surface area Li deposits and high Coulombic efficiency, despite the fact that the SEI is thicker and chemically more heterogeneous than LiTFSI alone. These data suggest that SEI design strategies that increase SEI stability and Li interfacial exchange rate will lead to more even current distribution, ultimately providing a new framework to generate smooth Li morphologies during plating/stripping. File list (2) download file view on ChemRxiv SEItransportv29_acceptedchanges.pdf (840.92 KiB) download file view on ChemRxiv SEItransportSI_v16.pdf (2.12 MiB)

The high-voltage LiNi 0.5 Mn 1.5 O 4 (LNMO) spinel cathode material offers high energy density storage capabilities without the use of costly Co that is prevalent in other Li-ion battery chemistries (e.g., LiNi x Mn y Co z O 2 (NMC)). Unfortunately, LNMO-containing batteries suffer from poor cycling performance because of the intrinsically coupled processes of electrolyte oxidation and transition metal dissolution that occurs at high voltage. In this work, we use operando electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR) spectroscopies to demonstrate that transition metal dissolution in LNMO is tightly coupled to HF formation (and thus, electrolyte oxidation reactions as detected with operando and in situ solution NMR), indicative of an acid-driven disproportionation reaction that occurs during delithiation (i.e., battery charging). Leveraging the temporal resolution (s-min) of magnetic resonance, we find that the LNMO particles accelerate the rate of LiPF 6 decomposition and subsequent Mn 2+ dissolution, possibly due to the acidic nature of terminal Mn-OH groups. X-ray photoemission electron microscopy (XPEEM) provides surfacesensitive and localized X-ray absorption spectroscopy (XAS) measurements, in addition to X-ray photoelectron spectroscopy (XPS), that indicate disproportionation is enabled by surface reconstruction upon charging, which leads to surface Mn 3+ sites on the LNMO particle surface that can disproportionate into Mn 2+ (dissolved) and Mn 4+ (s) . During discharge of the battery, we observe high quantities of metal fluorides (in particular, MnF 2 ) in the cathode electrolyte interphase (CEI) on LNMO as well as the conductive carbon additives in the composite. Electronic conductivity measurements indicate that the MnF 2 decreases film conductivity by threefold compared to LiF, suggesting that this CEI component may impede both the ionic and electronic properties of the cathode. Ultimately, to prevent transition metal dissolution and the associated side reactions in spinel-type cathodes (particularly those that operate at high voltages like LNMO), the use of electrolytes that offer improved anodic stability and prevent acid byproducts will likely be necessary.

The high specific capacities of Ni-rich transition metal oxides have garnered immense interest for improving the energy density of Li-ion batteries (LIBs). Despite the potential of these materials, Ni-rich cathodes suffer from interfacial instabilities that lead to crystallographic rearrangement of the active material surface as well as the formation of a cathode electrolyte interphase (CEI) layer on the composite during electrochemical cycling. While changes in crystallographic structure can be detected with diffraction-based methods, probing the chemistry of the disordered, heterogeneous CEI layer is challenging. In this work, we use a combination of ex situ solid-state nuclear magnetic resonance (SSNMR) spectroscopy and X-ray photoemission electron microscopy (XPEEM) to provide chemical and spatial information on the CEI deposited on LiNi0.8Mn0.1Co0.1O2 (NMC811) composite cathode films. Specifically, XPEEM elemental maps offer insight into the lateral arrangement of the electrolyte decomposition products that comprise the CEI and paramagnetic interactions (assessed with electron paramagnetic resonance (EPR) and relaxation measurements) in 13 C SSNMR provide information on the radial arrangement of the CEI from the NMC811 particles outward. Using this approach, we find that LiF, Li2CO3, and carboxy-containing structures are directly appended to NMC811 active particles, whereas soluble species detected during in situ 1 H and 19 F solution NMR experiments (e.g., alkyl carbonates, HF, and vinyl compounds) are randomly deposited on the composite surface. We show that the combined approach of ex situ SSNMR and XPEEM, in conjunction with in situ solution NMR, allows spatially-resolved, molecular-level characterization of paramagnetic surfaces and new insights into electrolyte oxidation mechanisms in porous electrode films.

The dynamic behavior of the interface between the lithium metal electrode and a solid-state electrolyte plays a critical role in all-solid-state battery performance. The evolution of this interface throughout cycling involves multiscale mechanical and chemical heterogeneity at the micro- and nano-scale. These features are dependent on operating conditions such as current density and stack pressure. Here we report the coupling of operando acoustic transmission measurements with nuclear magnetic resonance spectroscopy and magnetic resonance imaging to correlate changes in interfacial mechanics (such as contact loss and crack formation) with the growth of lithium microstructures during cell cycling. Together, the techniques reveal the chemo-mechanical behavior that governs lithium metal and Li7La3Zr2O12 interfacial dynamics at various stack pressure regimes and with voltage polarization.

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Here, we investigate the recovery and reuse of polyvinylidene fluoride (PVDF) binders from both homemade and commercial cathode films in Li ion batteries. We find that PVDF solubility depends on whether the polymer is an isolated powder or cast into a composite film. A mixture of tetrahydrofuran:N‐methyl‐2‐pyrrolidone (THF : NMP, 50 : 50 v/v) at 90 °C delaminates composite cathodes from Al current collectors and yields pure PVDF as characterized by 1 H nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), wide‐angle X‐ray scattering (WAXS), and scanning electron microscopy (SEM). PVDF recovered from Li ion cells post‐cycling exhibits similar performance to pristine PVDF. These data suggest that PVDF can be extracted and reused during Li ion battery recycling while simultaneously eliminating the formation of HF etchants, providing an incentive for use in direct cathode recycling.