Solution NMR of Battery Electrolytes: Assessing and Mitigating Spectral Broadening Caused by Transition Metal...

NMR spectroscopy is a powerful tool that is commonly used to assess the degradation of lithium-ion battery electrolyte solutions. However, dissolution of paramagnetic Ni²⁺ and Mn²⁺ ions from cathode materials may affect the NMR spectra of the electrolyte solution, with the unpaired electron spins in these paramagnetic solutes inducing rapid nuclear relaxation and spectral broadening (and often peak shifts). This work establishes how dissolved Ni²⁺ and Mn²⁺ in LiPF₆ electrolyte solutions affect ¹H, ¹⁹F, and ³¹P NMR spectra of pristine and degraded electrolyte solutions, including whether the peaks from degradation species are at risk of being lost and whether the spectral broadening can be mitigated. Mn²⁺ is shown to cause far greater peak broadening than Ni²⁺, with the effect of Mn²⁺ observable at just 10 μM. Generally, ¹⁹F peaks from PF₆ ^- degradation species are most affected by the presence of the paramagnetic metals, followed by ³¹P and ¹H peaks. Surprisingly, when NMR solvents are added to acquire the spectra, the degree of broadening is heavily solvent-dependent, following the trend of solvent donor number (increased broadening with lower solvent donicity). Severe spectral broadening is shown to occur whether Mn is introduced via the salt Mn(TFSI)₂ or is dissolved from LiMn₂O₄. We show that the weak ¹⁹F and ³¹P peaks in spectra of electrolyte samples containing micromolar levels of dissolved Mn²⁺ are broadened to an extent that they are no longer visible, but this broadening can be minimized by diluting electrolyte samples with a suitably coordinating NMR solvent. Li₃PO₄ addition to the sample is also shown to return ¹⁹F and ³¹P spectral resolution by precipitating Mn²⁺ out of electrolyte samples, although this method consumes any HF in the electrolyte solution.