Titration Mass Spectroscopy (TMS): A Quantitative Analytical Technology for Rechargeable Batteries

Abstract

Development of high-energy-density rechargeable battery systems not only needs advanced qualitative characterizations for mechanism exploration but also requires accurate quantification technology to quantitatively elucidate products and fairly assess numerous modification strategies. Herein, as a reliable quantification technology, titration mass spectroscopy (TMS) is developed to accurately quantify O-related anionic redox reactions (Li−O 2 battery and nickel-cobalt-manganese (NCM)/Li-rich cathodes), parasitic carbonate deposition and decomposition (derived from airexposure degradation and electrolyte oxidation), and dead Li 0 formation (Limetal battery and over-discharged graphite anode). TMS technology can harvest key information on products (e.g., quantification of oxidized lattice oxygen and solid electrolyte interphase (SEI)/cathode electrolyte interphase (CEI) components) and guide corresponding design strategy by enhancing understanding of the mechanism (e.g., clearly distinguish the catalytic target of highly oxidative Ni 4+ on the NCM cathode). Not limited as a rigid quantification tool for widely known products/mechanisms, TMS technology has been demonstrated as a powerful and versatile tool for the investigations of advanced batteries.

Full-Dimensional Analysis of Electrolyte Decomposition on Cathode–Electrolyte Interface: Establishing Characterization Paradigm on LiNi0.6Co0.2Mn0.2O2 Cathode with Potential Dependence

“…Oxygen release above 4.5 V could be attributed to singlet oxygen from nickel manganese cobalt oxide (NCM) cathode materials, which originated from the reactive lattice oxygen in the near-surface region through activation, and the possibility of cathode surface reconstruction cannot be ruled out. 25 And the evolution of CO 2 and CO below 4.5 V is attributed to acid−base reactions between proton species and formed carbonate species attached to NMC622 particles as well as the hydrolysis of the carbonate solvents. 26 The observed CO 2 and CO above 4.5 V are mainly due to irreversible electrolyte decomposition, in which reactive lattice oxygen in the near-surface region attacks electrolyte.…”

“…During charging from 4.5 to 4.8 V, the CO 2 to CO ratio increased proportionally with voltages; meanwhile, all signals were approaching their maximums. Oxygen release above 4.5 V could be attributed to singlet oxygen from nickel manganese cobalt oxide (NCM) cathode materials, which originated from the reactive lattice oxygen in the near-surface region through activation, and the possibility of cathode surface reconstruction cannot be ruled out . And the evolution of CO 2 and CO below 4.5 V is attributed to acid–base reactions between proton species and formed carbonate species attached to NMC622 particles as well as the hydrolysis of the carbonate solvents .…”

Recent progress and perspectives on cation disordered rock-salt material for advanced Li-ion batteries

“…To accurately quantify the anionic redox in DRX materials, the titration mass spectrometry (TMS) detection method has been introduced into the study of batteries and has been fully applied. 130 TMS serves as a reliable quantification technique for the accurate quantification of O-related anionic redox reactions. TMS technology can achieve the quantification of oxidized lattice oxygen and the solid electrolyte interphase (SEI)/cathode electrolyte interphase (CEI) and guide corresponding design strategies by enhancing the understanding of the mechanism.…”

Quantifying the Influence of Li Plating on a Graphite Anode by Mass Spectrometry

“…In this study, we employed an online electrochemical mass spectrometry (OEMS) method − to clearly and accurately detect the onset of microscale Li plating in real time based on H 2 evolution capture from the reaction of plated Li with the polymer binder. Moreover, the titration mass spectrometry (TMS) method , was used to analyze quantitatively the influence of Li plating on the SEI components, dead Li, and other irreversible capacity assignments. Based on the established characterization paradigm of the combination of OEMS and TMS, the role of traditional vinylene carbonate (VC) and/or fluoroethylene carbonate (FEC) additives is recognized at the level of Li plating/stripping for the Gr anode.…”