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@ARTICLE{Kubot:1025932,
      author       = {Kubot, Maximilian and von Holtum, Bastian and Winter,
                      Martin and Wiemers-Meyer, Simon and Nowak, Sascha},
      title        = {{O}rganofluorophosphates as {O}xidative {D}egradation
                      {P}roducts in {H}igh-{V}oltage {L}ithium {I}on {B}atteries
                      with {NMC} or {LNMO} {C}athodes},
      journal      = {Journal of the Electrochemical Society},
      volume       = {169},
      number       = {11},
      issn         = {0013-4651},
      address      = {Bristol},
      publisher    = {IOP Publishing},
      reportid     = {FZJ-2024-03210},
      pages        = {110534 -},
      year         = {2022},
      abstract     = {Organofluorophosphates (OFPs) have been reported to pose
                      substantial health hazards due to their structural
                      similarities to pesticides and nerve agents. Formation of
                      OFPs in lithium ion batteries (LIBs) due to hydrolysis of
                      the conducting salt lithium hexafluorophosphate (LiPF6) and
                      the reaction with the organic carbonate solvents that make
                      up the electrolyte has been discussed in literature. The
                      oxidative formation of OFPs in electrolytes containing
                      fluoroethylene carbonate (FEC) and vinylene carbonate (VC)
                      as film-forming additives is presented in this study.
                      Further the impact of potentially reactive positive
                      electrode surfaces is investigated with the layered metal
                      oxide NCM622 which is ascribed to release reactive oxygen
                      species at high voltages and the spinel type LNMO as a
                      typical high-voltage material. Cycling of the self-assembled
                      LIB coin cells (CR2032) at cut-off voltages of 4.8 V gave
                      rise to a number of degradation products including
                      potentially highly toxic OFPs. Here, the presence of the
                      film-forming additive had a massive impact on the amount of
                      OFPs formed during electrochemical cycling experiments,
                      which raises further concerns for the utilization of
                      film-forming additives for high voltage applications. The
                      formation pathway of OFPs through EC-polymerization proposed
                      in literature is evaluated and an alternative mechanism with
                      FEC/VC as the carbonyl carbon-donor is presented. Structure
                      elucidation and separation of the formed OFPs is achieved by
                      utilization of reversed-phase (RP) chromatography hyphenated
                      to a high-resolution ion trap time-of-flight mass
                      spectrometer (IT-TOF-MS). The findings presented in this
                      study support further investigation of the formation of OFPs
                      in film-forming additive-containing electrolytes,
                      quantitative approaches and toxicological assessments due to
                      the highly toxic nature of OFPs.},
      cin          = {IEK-12},
      ddc          = {660},
      cid          = {I:(DE-Juel1)IEK-12-20141217},
      pnm          = {1221 - Fundamentals and Materials (POF4-122) / BMBF
                      03XP0311B - BatgasMod - Batteriegasungs-Modellierung
                      (03XP0311B)},
      pid          = {G:(DE-HGF)POF4-1221 / G:(BMBF)03XP0311B},
      typ          = {PUB:(DE-HGF)16},
      UT           = {WOS:000889361400001},
      doi          = {10.1149/1945-7111/aca2e8},
      url          = {https://juser.fz-juelich.de/record/1025932},
}