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9 protocols using 1 2 dimethoxyethane

1

Coin Cell Assembly for Electrochemical Measurements

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For electrochemical measurements, 2032-type coin cells (MTI Corporation)
were assembled in an argon-filled glovebox. The prepared sample and
lithium foil (Alfa Aesar) were used as the working and counter/reference
electrodes, respectively. The typical mass loading of the active material
was approximately 1.0 mg cm–2. The electrolyte was
prepared by dissolving 1 M LiTFSI in cosolvents of 1,3-dioxolane (anhydrous,
contains ∼75 ppm butylated hydroxytoluene as an inhibitor,
99.8%, Sigma-Aldrich) and 1,2-dimethoxyethane (anhydrous, 99.5%, Sigma-Aldrich)
at a volume ratio of 1:1. Before preparing the electrolyte, the solvents
were placed in molecular sieves for 24 h to remove moisture. Polypropylene
membranes (Celgard Inc.) were used as separators. Galvanostatic measurements
were performed in the potential range of 1.0–3.0 V vs Li/Li+ using a battery cycler (WonATech WBS3000). For the rate capability
tests, the charge rate was fixed at 0.5 C in the constant-current
mode, and the discharge rate was varied from 0.5 to 10 C (1 C = 1675
mA g–1). CV measurements were obtained in the potential
range of 1.0–3.0 V vs Li/Li+ at a scan rate of 0.1
mV s–1 using a multichannel battery tester (Biologic
VMP3). All electrochemical measurements were conducted at 25 °C.
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2

Characterization of Li-Metal Electrode Morphology

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The morphology of the Li-metal
electrodes was examined by field-emission
SEM (Sirion, FEI). In a dry glovebox filled with argon, the Li-metal
electrodes were carefully separated from the disassembled cells after
electrochemical investigations. To remove any residual electrolyte,
the obtained electrodes were gently rinsed with 1,2-dimethoxyethane
(anhydrous, 99.5%, Sigma-Aldrich, USA) and dried under vacuum overnight.
The samples were vacuum-sealed in a PP bottle for safe transfer without
contamination and exposed to air only for a few seconds at sample
loading. To prevent Li-metal contamination, the bonding characterizations
of the electrode surface were carried out via FT-IR (IFS66V/S-HYPERION
300, Bruker Optic) and XPS (Sigma Probe, Thermo VG Scientific) in
a vacuum chamber. The FT-IR analysis was carried out in the wave number
range of 2000–900 cm–1, and XPS spectra were
calibrated against the hydrocarbon peak at a binding energy of 285.0
eV.
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3

Synthesis of Lithium-Sulfur Battery Materials

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Sublimed sulfur (≥99.5%), bis(trifluoromethane)sulfonimide lithium salt (LiTFSI), anhydrous lithium nitrate, dioxolane (DOL, 99%) 1,2-dimethoxyethane (anhydrous DME, 99.5%), and analytical grade chemicals such as KMnO4 were procured from Sigma Aldrich. Polyvinylidene fluoride (PVDF), N-methyl pyrrolidinone (NMP) and Super P were purchased from Alfa Aesar. l-glycine was procured from Fischer Scientific. All chemicals were used as received without further purification.
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4

Synthesis of Electrochemical Devices

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Sublimed sulfur powder,
lithium nitrate (LiNO3), dopamine hydrochloride, potassium
ferricyanide (III), anhydrous
ethanol, bis(trifluoromethane)sulfonimide lithium salt (LiTFSI), polyvinylidene
fluoride (PVDF), N-methyl-2-pyrrolidone (NMP), 1-vinylimidazole
(≥99%), 1-bromodecane (98%), 1,2-dimethoxyethane (DME), carbon
disulfide, tris(hydroxymethyl) aminomethane (Tris), and 1,3-dioxolane
(DOL) were purchased from Sigma-Aldrich. Hydrochloric acid solution
(37%) and melamine were purchased from Alfa-Aesar. Water-soluble nonionic
azo initiator 2,2′-azobis[2-methyl-N-(2-hydroxyethyl)
propionamide] (VA086) was obtained from Wako Chemicals. All chemicals
were used without any further purification.
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5

Synthesis of Ferrocene Ionic Liquids

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1-Vinylimidazole (99%) and sodium tetrafluoroborate were obtained from Alfa Aesar. Potassium hexafluorophosphate was purchased from Acros Organics. 1,1′-Ferrocene dicarboxylic acid was bought from Energy Chemical. Bromoacetonitrile (95%) was purchased from TCI Europe. Lithium bis(trifluoromethane sulfonyl)imide (LiTFSI, 99.95%) was purchased from Io-li-tec. Lithium nitrate (LiNO3), polyvinylidene fluoride (PVDF), N-methyl-2-pyrrolidone (NMP), 1,2-dimethoxyethane (DME), and 1,3-dioxolane (DOL) were purchased from Sigma-Aldrich. Sulfur powder was purchased from Alfa Aesar. All chemicals were used without any further purification. Solvents were of analytical grade.
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6

Lithium-Sulfur Battery Material Preparation

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Poly(vinylidene fluoride) (PVDF), lithium bis(trifluoromethane) sulfonamide (LiTFSI), lithium hexafluoro phosphate (LiPF6), ethylene carbonate (EC), propylene carbonate, 1,2‐dimethoxyethane (DME), 1,3‐dioxolane (DOL), dimethyl carbonate, ethyl methyl carbonate, N‐methyl‐2‐pyrrolidone (NMP), potassium hydroxide (KOH), PAN and PPS were purchased from Sigma‐Aldrich. The sulfur (S) powder (325 mesh) was purchased from Alfa Aesar. Carbon super P, lithium chips/foil, and carbon coated Al‐foil (Thickness 18 µm) were purchased from MTI Corporation (mtixtl.com) Bucky papers (60 gsm) were obtained from Nanotech Labs, Yadkinville, NC.
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7

Nanomyte BE-70 Sulfur Electrode Fabrication

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Nanomyte BE-70 sulfur positive
electrodes were procured from the NEI Corporation, USA. The electrodes,
composed of 70 wt % sulfur, 10 wt % polyvinylidene fluoride binder,
and 20 wt % carbon black, were used as received. The active loading
of sulfur was 3.4 mg cm–2 (thickness 55 μm).
Lithium disks (15.6 mm diameter and 0.45 mm thickness) were purchased
from PI-KEM Ltd. For electrolyte preparation, 1,2-dimethoxyethane
(DME), 1,3-dioxolane (DOL) solvents, lithium bis(trifluoromethanesulfonyl)imide
(LiTFSI), and lithium nitrate (LiNO3) salts were provided
by Sigma-Aldrich. Lithium sulfide and sulfur, used for polysulfide
synthesis, were also procured from Sigma-Aldrich. Fibroin (Fancci,
molecular weight >200,000 Da) was purchased from Simatech Inc.,
China.
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8

Synthesis of Lithium Sulfur Batteries

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All chemicals were used as received. Cobalt nitrate hexahydrate (Co(NO3)2·6H2O, 99.99%), thiourea (H2NCSNH2, 99%), sodium dodecyl sulfate (CH3(CH2)11OSO3Na, 99%), sodium hydrosulfide hydrate (NaHS·xH2O, NaHS ≥ 60%), sodium hydroxide (NaOH, 98%), 1,3-dioxolane (DOL, 99.8 wt%), 1,2-dimethoxyethane (DME, 99.5 wt%), lithium bis(trifluoromethanesulfonyl) imide (LiTFSI, 99.95 wt%), lithium nitrate (LiNO3, 99.99%), lithium sulfide (Li2S, 99.98%) and sulfur (S, flakes, 99.99%) were purchased from Sigma-Aldrich. Ultrapure water (UPW) filtered by a Millipore Milli-Q Integral Water Purification System (Millipore Corp.) was used as the common solvent.
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9

Lithium-Sulfur Battery Components Preparation

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Melamine (99%), cyanuric acid (98%), 1,3-dioxolane (DOL, 99.8%), 1,2-dimethoxyethane (DME, 99.5%), lithium bis(trifluoromethylsulfonyl)imide (LiTFSI, 99.5%), and sulfur (99.5%) were purchased from Sigma-Aldrich (Darmstadt, Germany). Lithium sulfide (Li2S, 99.9%), lithium nitrate (LiNO3, 99.99%), and lithium metal (99.9%) were purchased from Alfa Aesar (Haverhill, MA, USA). N-methyl pyrrolidone (NMP, 99.0%, DAEJUNG Co., Siheung, Korea), polyvinylidene fluoride (PVdF, MTI Co., Richmond, CA, USA), Super P (Timcal Co., Bodio, Switzerland), dimethyl sulfoxide (DMSO, 99.5%, DAEJUNG Co., Siheung, Korea), glucose (98%, JUNSEI Co., Tokyo, Japan), and ethanol (94.5%, DAEJUNG Co., Siheung, Korea) were also used. All the reagents were purchased commercially and used without purification.
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