X-ray Raman spectroscopy of lithium-ion battery electrolyte solutions in a flow cell

The effects of varying LiPF₆ salt concentration and the presence of lithium bis­(oxalate)borate additive on the electronic structure of commonly used lithium-ion battery electrolyte solvents (ethyl­ene carbonate–di­methyl carbonate and propyl­ene carbonate) have been investigated. X-ray Raman scattering spectroscopy (a non-resonant inelastic X-ray scattering method) was utilized together with a closed-circle flow cell. Carbon and oxygen K-edges provide characteristic information on the electronic structure of the electrolyte solutions, which are sensitive to local chemistry. Higher Li⁺ ion concentration in the solvent manifests itself as a blue-shift of both the π* feature in the carbon edge and the carbonyl π* feature in the oxygen edge. While these oxygen K-edge results agree with previous soft X-ray absorption studies on LiBF₄ salt concentration in propyl­ene carbonate, carbon K-edge spectra reveal a shift in energy, which can be explained with differing ionic conductivities of the electrolyte solutions.