Abstract
Solid-state electrolytes are regarded as an attractive alternative to liquid electrolytes in lithium batteries because of their intrinsic safety features and mechanical strength; however maintaining high bulk and interfacial ion fluxes in scalable electrolyte chemistries remains a significant challenge. In this work, we report on synthesis and electrochemical features of a class of solid-state hybrid polymer electrolytes comprised of silica nanoparticles with grafted poly(ethylene oxide) chains. By regulating the salt content in the materials, we find that it is possible to drive microstructural changes, including nanoparticle arrangements, to achieve appreciable levels of room-temperature ionic conductivity in a solid-state polymer composite. Additionally, we show that rationally designed salt additives can be used to create cathode-electrolyte interphases (CEI) that increase the oxidative stability of PEO-based electrolytes. In so doing, we report that solid-state lithium batteries comprised of a high-voltage nickel manganese cobalt oxide cathode, a metallic Li anode, and a solid-state hybrid polymer electrolyte can be cycled stably with high levels of reversibility.
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Acknowledgments
The authors acknowledge support of the National Science Foundation, Division of Materials Research, through Award No. DMR-1609125. This work made use of the Cornell Center for Materials Research Shared Facilities, which are supported through the NSF MRSEC program (DMR-1719875).
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Appendix: Supplementary Information
Appendix: Supplementary Information
9.1.1 Materials and Methods
9.1.1.1 Synthesis of Self-Suspended Covalently Grafted Hairy Nanoparticles
Self-suspended covalently grafted nanoparticles were prepared using a previously described method. Briefly, these nanoparticles are prepared using a two-step process, in which polyethylene oxide was first functionalized with a silane group by reacting the isocyanate end in 3-(triethoxysilyl) propyl isocyanate (Sigma-Aldrich) with the amine end in amino-polyethylene oxide (MW ≈ 5000 Da, PDI ≈ 1.1, purchased from Laysan Bio) in a stoichiometric ratio, creating a urethane bond in the process. The prepared silane functionalized polymer was condensed onto silica nanoparticles with diameter 25 ± 2 nm by reaction with the hydroxyl groups on the surface of the particles (TM-50, Sigma-Aldrich). Excess unreacted polymer chains were removed by repeated centrifugation in a chloroform-hexane mixture. The inorganic content of these hairy nanoparticles was analyzed using thermogravimetric analysis (TGA) on a TGA Q1000 (TA Instruments). The TGA for different samples revealed inorganic content of 51% corresponding to grafting density of approximately 1.47 chains/nm2.
9.1.1.2 Characterization
Glassy electrolytes were prepared by mixing the hairy nanoparticles with predetermined amount of LiTFSI salt (Sigma-Aldrich). The molecular structuring in the glassy electrolytes was studied using attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) on a Nicolet iS10 FTIR spectrometer (Thermo Fisher Scientific) equipped with a deuterated triglycine sulfate (DTGS) detector and a SMART iTR diamond ATR accessory. Melting transitions were then investigated using differential scanning calorimetry on a DSC Q2000 (TA Instruments) at a scan rate of 10 °C/min. Morphology of the electrolytes at the electrode-electrolyte interface was studied using scanning electron microscope (Zeiss Gemini 500) at the Cornell Centre for Materials Research (CCMR). Fourier transform infrared spectroscopy (ATR-FTIR) was performed on a Nicolet iS10 FTIR spectrometer (Thermo Fisher Scientific) equipped with a deuterated triglycine sulfate (DTGS) detector and a SMART iTR diamond ATR accessory.
9.1.1.3 Electrochemical Measurements
2030 coin-type cells were assembled in a glovebox (MBraun Labmaster) with Nickel Cobalt Manganese Oxide (NCM) Cathode (2 mA/cm2) as the cathode and lithium foil (Alfa Aesar) as the anode. The NCM cathode has 80% active material (NCM 622), 10% binder (PTFE), and 10% carbon. The active material loading was ~11 mg/cm2. The glassy electrolyte was sandwiched between the two electrodes, after wetting the cathode in a liquid electrolyte comprised of LiBOB (Oakwood Chemicals), LiTFSI (Sigma-Aldrich), and LiPF6 (Sigma-Aldrich) salts in an ethylene carbonate/dimethyl carbonate (Sigma-Aldrich) mixture.
Ionic transport in the bulk and at the interface in this system was studied using conductivity and impedance measurements using a Novocontrol N40 broadband spectrometer fitted with a Quarto temperature control system. The samples were sandwiched between two gold-plated blocking electrodes. The cyclic voltammetry was done in lithium versus stainless steel configuration using a CHI600 potentiostat. The cycling characteristics of the cells were evaluated under galvanostatic conditions using Neware CT-3008 battery testers.
9.1.1.4 Small-Angle X-Ray Scattering Measurements
X-ray scattering (SAXS) measurements were performed on the solventless SiO2-PEGME nanoparticles at sector 12-ID-B of Argonne National Laboratory, using a point collimated X-ray beam. The sample was smeared on a thermal cell, and the measurements were performed at different temperatures, all above melting point of PEG. The measured scattering intensity, I(q), depends on wave vector q and particle volume fraction φ as
where P(q) and S(q, φ) represent the particle form factor and the interparticle structure factor, respectively. Because in the limit of infinite dilution S(q, φ → 0) ≈ 1, the particle form factor can thus be obtained from the scattering intensities of dilute aqueous suspensions of particles. The structure factor can then be obtained by normalizing the scattering intensity with the form factor.
9.1.1.5 Rheology Measurements
Rheology measurements. Oscillatory shear rheology measurements were performed at a temperature of 90 °C using a Physica MCR 501 rheometer (Anton Paar at Cornell Energy Systems Institute (CESI)), outfitted with a cone and plate geometry (10 mm diameter, 2° cone angle). To study the linear and nonlinear viscoelastic properties of the materials, variable strain amplitude measurements at a fixed angular frequency of ω = 10 rad/s as well as variable frequency measurements at a fixed strain amplitude γ = 0.5% were employed.
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Choudhury, S. (2019). Soft Colloidal Glasses as Solid-State Electrolytes. In: Rational Design of Nanostructured Polymer Electrolytes and Solid–Liquid Interphases for Lithium Batteries. Springer Theses. Springer, Cham. https://doi.org/10.1007/978-3-030-28943-0_9
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