In situ Raman spectroscopy and cyclic voltammetry were used to investigate the mechanism of sulfur reduction in lithium-sulfur battery slurry cathodes with 1 M lithium bis(trifluoromethane sulfonyl)imide (LiTFSI) and tetraethylene glycol dimethyl ether (TEGDME)/1,3-dioxolane (DIOX) (1/1, v/v). Raman spectroscopy shows that long-chain polysulfides (S8(2-)) were formed via S8 ring opening in the first reduction process at ∼2.4 V vs Li/Li(+) and short-chain polysulfides such as S4(2-), S4(-), S3(•-), and S2O4(2-) were observed with continued discharge at ∼2.3 V vs Li/Li(+) in the second reduction process. Elemental sulfur can be reformed in the end of the charge process. Rate constants obtained for the appearance and disappearance polysulfide species shows that short-chain polysulfides are directly formed from S8 decomposition. The rate constants for S8 reappearance and polysulfide disappearance on charge were likewise similar. The formation of polysulfide mixtures at partial discharge was found to be quite stable. The CS2 additive was found to inhibit the sulfur reduction mechanism allowing the formation of long-chain polysulfides during discharge only and stabilizing the S8(2-) product.

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Li and 33 S solid-state magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy were used to identify the discharge products in lithium-sulfur (Li-S) battery cathodes. Cathodes were stopped at different potentials throughout battery discharge and measured ex-situ to obtain chemical shifts and T 2 relaxation times of the products formed. The chemical shifts in the spectra of both 6 Li and 33 S NMR demonstrate that long-chain, soluble lithium polysulfide species formed at the beginning of discharge are indistinguishable from each other (similar chemical shifts), while short-chain, insoluble polysulfide species that form at the end of discharge (presumably Li 2 S 2 and Li 2 S) have a different chemical shift, thus distinguishing them from the soluble long-chain products. T 2 relaxation measurements of discharged cathodes were also performed which resulted in two groupings of T 2 times that follow a trend and support the previous conclusions that long-chain polysulfide species are converted to shorter chain species during discharge. Through the complementary techniques of 1-D 6 Li and 33 S solid-state MAS NMR spectroscopy, solution 7 Li and 1 H NMR spectroscopy, and T 2 measurements, structural information about the discharge products of Li-S batteries is obtained.

Solid-state (7)Li and (13)C MAS NMR spectra of cycled graphitic Li-ion anodes demonstrate SEI compound formation upon lithiation that is followed by changes in the SEI upon delithiation. Solid-state (13)C DPMAS NMR shows changes in peaks associated with organic solvent compounds (ethylene carbonate and dimethyl carbonate, EC/DMC) upon electrochemical cycling due to the formation of and subsequent changes in the SEI compounds. Solid-state (13)C NMR spin-lattice (T1) relaxation time measurements of lithiated Li-ion anodes and reference poly(ethylene oxide) (PEO) powders, along with MALDI-TOF mass spectrometry results, indicate that large-molecular-weight polymers are formed in the SEI layers of the discharged anodes. MALDI-TOF MS and NMR spectroscopy results additionally indicate that delithiated anodes exhibit a larger number of SEI products than is found in lithiated anodes.

In situ EQCM experiments were used to investigate the stability and roughness changes occurring in a sulfur-carbon cathode utilized for a Li-S battery during the charge-discharge process. Results show that the sulfur-carbon cathode gains mass during the first discharge plateau (∼2.4 V) due to the formation of the long chain polysulfides during the discharge (lithiation) process. However, further discharge to below 2.4 V yields an increase in the crystal resistance (Rc) suggesting the sulfur-carbon cathode becomes rougher. During the charge (delithiation) process, the roughness of the sulfur-carbon cathode decreases. Time dependent measurements show that the electrode surface becomes rougher with the deeper discharge, with the change occurring following a step to 1.5 V. The sulfur-carbon cathode exhibits stable Rc and frequency behavior initially, but then becomes rougher in subsequent following cycles.