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. 2023 Jul 31;26(9):107517.
doi: 10.1016/j.isci.2023.107517. eCollection 2023 Sep 15.

Laser desorption/ionization-mass spectrometry for the analysis of interphases in lithium ion batteries

Valentin Göldner  1   2 , Linda Quach  2   3 , Egy Adhitama  2   4 , Arne Behrens  1   5 , Luisa Junk  1 , Martin Winter  2   4   6 , Tobias Placke  2   4 , Frank Glorius  2   3 , Uwe Karst  1   2
Affiliations

Laser desorption/ionization-mass spectrometry for the analysis of interphases in lithium ion batteries

Valentin Göldner et al. iScience. .

Abstract

Laser desorption/ionization-mass spectrometry (LDI-MS) is introduced as a complementary technique for the analysis of interphases formed at electrode|electrolyte interfaces in lithium ion batteries (LIBs). An understanding of these interphases is crucial for designing interphase-forming electrolyte formulations and increasing battery lifetime. Especially organic species are analyzed more effectively using LDI-MS than with established methodologies. The combination with trapped ion mobility spectrometry and tandem mass spectrometry yields additional structural information of interphase components. Furthermore, LDI-MS imaging reveals the lateral distribution of compounds on the electrode surface. Using the introduced methods, a deeper understanding of the mechanism of action of the established solid electrolyte interphase-forming electrolyte additive 3,4-dimethyloxazolidine-2,5-dione (Ala-N-CA) for silicon/graphite anodes is obtained, and active electrochemical transformation products are unambiguously identified. In the future, LDI-MS will help to provide a deeper understanding of interfacial processes in LIBs by using it in a multimodal approach with other surface analysis methods to obtain complementary information.

Keywords: Analytical Electrochemistry; Electrochemical energy storage; Interfacial electrochemistry; Organic chemistry.

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Conflict of interest statement

The authors declare no competing interests.

Figures

None
Graphical abstract
Figure 1
Figure 1
Proposed reaction for electrochemical oligomerization of 3,4-dimethyloxazolidine-2,5-dione (Ala-N-CA)
Figure 2
Figure 2
LDI-MS spectra obtained by analysis of of electrode surfaces (A) Pristine electrode. (B) Electrode cycled with the baseline electrolyte (LP57). (C) Electrode cycled with Ala-N-CA additive-containing electrolyte.
Figure 3
Figure 3
Results from LDI-TIMS-MS and LDI-TIMS-MS/MS analysis of Ala-N-CA-derived oligomers (A) Heatmap depicting the LDI-TIMS-MS data obtained from an electrode cycled with Ala-N-CA-containing electrolyte. (B) Heatmap obtained by TIMS-bbCID analysis of the same electrode. (C) Heatmap obtained by prm-PASEF analysis of electrochemically formed Ala-N-CA oligomers on the same electrode. (D) Extracted ion mobilograms from LDI-TIMS-MS analysis of differently sized electrochemical Ala-N-CA oligomers. (E) Fragment spectrum of the electrochemically formed heptamer (m/z 576.4051) extracted from the prm-PASEF dataset within the inverse reduced mobility range 1.069–1.113 V s cm−2. (F) Fragmentation pattern of the electrochemically formed Ala-N-CA heptamer.
Figure 4
Figure 4
Proposed mechanism for the electrochemically initiated oligomerization of Ala-N-CA
Figure 5
Figure 5
Mass spectrometric images of a Si/graphite electrode after three cycles with Ala-N-CA-containing electrolyte in Si/graphite || Li-metal cells Images of (A) the electrochemically formed dimer (m/z 151.1419, green), (B) the electrochemically formed tetramer (m/z 321.2467, orange), (C) the electrochemically formed hexamer (m/z 491.3535, red) and (D) the electrochemically formed nonamer (m/z 746.5114, turquoise).
See this image and copyright information in PMC

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