Online sample pretreatment for analysis of decomposition products in lithium ion battery by liquid chromatography hyphenated with ion trap-time of flight-mass spectrometry or inductively coupled plasma-sector field-mass spectrometry.

Lithium ion batteries are essential power sources for mobile electronic devices like cell phones, tablets and increasingly used in the field of electromobility and energy transition. The commonly applied liquid electrolytes in commercial cells contain a conducting salt at relatively high concentration (LiPF6, ≥1 mol/L). For analytical battery electrolyte investigations, it is necessary to protect the column and mass spectrometer from salt precipitation and clogging. Thus, dilution of the sample is necessary which results in higher limits of detection and limits of quantification. In this study, a comprehensive online sample preparation approach for reversed phase liquid chromatography with an online-solid phase extraction was developed, which allows higher injections volumes and lower dilution factors. For the method development of the online-solid phase extraction, pristine electrolytes were used with trimethyl phosphate and triethyl phosphate as model substances for organo(fluoro)phosphates with weak and strong retention on the extraction column. Organo(fluoro)phosphates are potential hazardous decomposition products, due to their structural similarity to chemical warfare agents like sarin, and therefore their quantification is beneficial for toxicological assessment. The optimization of chromatographic parameters was performed using electrochemically aged electrolytes. For substance independent quantification with a plasma-based technique, an isocratic separation method was implemented. Using optimized conditions, LiPF6 could be removed quantitatively and the injection volume was increased up to a factor of 50, while the dilution factor could be decreased up to a factor of ten. Eleven different organo(fluoro)phosphates with an overall concentration of 133 mg/kg were found. Therefore, limit of detection and limit of quantification were improved significantly (LOQ: ≤100 µg kg-1 phosphorus content, LOD: ≤35 µg kg-1 phosphorus content). In summary, a fast online sample preparation for liquid chromatographic investigations of lithium ion battery electrolytes was implemented, validated on electrochemically aged lithium ion battery electrolyte.

Application of large volume injection for sensitive LC-MS/MS analysis of seven artificial sweeteners in surface waters.

The combination of large volume injection and mixed-mode chromatography was performed for direct ultra-trace LC-MS/MS analysis of seven artificial sweeteners with varying physicochemical properties in surface water samples.•The injection volume was raised from 10 µL to 500 µL, while the overall analysis time was only increased by ≈5 min compared to the initial method.•Online column head refocusing and concentration of analytes enabled detection in sub-ng L-1 concentration range without elaborate sample preparation steps.•Relative standard deviations <7% despite multiple injection into the loop.

Fast sample preparation for organo(fluoro)phosphate quantification approaches in lithium ion battery electrolytes by means of gas chromatographic techniques.

Lithium ion batteries are essential power sources in portable electronics, electric vehicles and as energy storage devices for renewable energies. During harsh battery cell operation as well as at elevated temperatures, the electrolyte decomposes and inter alia organo(fluoro)phosphates are formed due to hydrolysis of the conducting salt lithium hexafluorophosphate (LiPF6). Since these phosphorus-containing decomposition products possess a potential toxicity based on structural similarities compared to chemical warfare agents, quantification is of high interest regarding safety estimates. In this study, two comprehensive approaches for the precipitation of highly concentrated PF6¯ were investigated, allowing the separation from target analytes (organo(fluoro)phosphates) and improving mass spectrometry-based quantification techniques. Trimethyl phosphate was used as a polar, non-acidic organophosphate reference substance for method development via liquid chromatography-mass spectrometry. Six solvents were examined regarding precipitation reaction and selectivity. Thermally degraded electrolytes were analyzed after precipitation by means of gas chromatography-flame ionization detector, demonstrating the applicability of the developed sample preparations. The optimized method was applied successfully without influencing any volatile and non-acidic decomposition products. Using optimized conditions, a precipitation rate of 98% PF6¯ was achieved. Consequently, a fast and easy sample preparation for gas chromatographic investigations on lithium ion battery electrolytes was implemented, applicable for routine analysis.

Clarification of Decomposition Pathways in a State-of-the-Art Lithium Ion Battery Electrolyte through 13 C-Labeling of Electrolyte Components.

The decomposition of state-of-the-art lithium ion battery (LIB) electrolytes leads to a highly complex mixture during battery cell operation. Furthermore, thermal strain by e.g., fast charging can initiate the degradation and generate various compounds. The correlation of electrolyte decomposition products and LIB performance fading over life-time is mainly unknown. The thermal and electrochemical degradation in electrolytes comprising 1 m LiPF6 dissolved in 13 C3 -labeled ethylene carbonate (EC) and unlabeled diethyl carbonate is investigated and the corresponding reaction pathways are postulated. Furthermore, a fragmentation mechanism assumption for oligomeric compounds is depicted. Soluble decomposition products classes are examined and evaluated with liquid chromatography-high resolution mass spectrometry. This study proposes a formation scheme for oligo phosphates as well as contradictory findings regarding phosphate-carbonates, disproving monoglycolate methyl/ethyl carbonate as the central reactive species.

Mn2+ or Mn3+ ? Investigating transition metal dissolution of manganese species in lithium ion battery electrolytes by capillary electrophoresis.

A new CE method with ultraviolet-visible detection was developed in this study to investigate manganese dissolution in lithium ion battery electrolytes. The aqueous running buffer based on diphosphate showed excellent stabilization of labile Mn3+ , even under electrophoretic conditions. The method was optimized regarding the concentration of diphosphate and modifier to obtain suitable signals for quantification. Additionally, the finally obtained method was applied on carbonate-based electrolytes samples. Dissolution experiments of the cathode material LiNi0.5 Mn1.5 O4 (lithium nickel manganese oxide [LNMO]) in aqueous diphosphate buffer at defined pH were performed to investigate the effect of a transition metal-ion-scavenger on the oxidation state of dissolved manganese. Quantification of both Mn species revealed the formation of mainly Mn3+ , which can be attributed to a comproportionation reaction of dissolved and complexed Mn2+ with Mn4+ at the surface of the LNMO structure. It was also shown that the formation of Mn3+ increased with lower pH. In contrast, dissolution experiments of LNMO in carbonate-based electrolytes containing LIPF6 showed only dissolution of Mn2+ .

Preparative hydrophilic interaction liquid chromatography of acidic organofluorophosphates formed in lithium ion battery electrolytes.

The expansion of lithium ion battery (LIB) application is accompanied by the growth of battery pack sizes. This progression emphasizes the consideration of electrolyte safety as well as environmental aspects in case of abuse, accident, or recycling. Hexafluorophosphate is one of the most commonly used conducting salt anions in electrolytes. It has great potential to degrade to various acidic and non-acidic organo(fluoro)phosphates with presence of water and during battery cell operation. Consequently, toxicological investigation on these organo(fluoro)phosphates has emerged because they either have structural similarities as chemical warfare agents or play a widespread physiological role as phosphates in the human body. This circumstance underlines the need of isolated examination of these compounds for safety assessment. In this work, we used hydrophilic interaction liquid chromatography for the extraction of acidic organofluorophosphates from thermally aged LIB electrolytes. The developed two-step fractionation method provided high separation selectivity towards acidic head groups, which allowed the separation of undesired matrix and target compounds. These findings facilitate isolated toxicological investigations on organofluorophosphates that are beneficial for environmental and safety research, the battery cell industry, and human safety surveillance in regard to aged LIB electrolytes.

Further Insights into Structural Diversity of Phosphorus-Based Decomposition Products in Lithium Ion Battery Electrolytes via Liquid Chromatographic Techniques Hyphenated to Ion Trap-Time-of-Flight Mass Spectrometry.

This study illustrates the high complexity of phosphorus-based decomposition products in thermally treated state-of-the-art lithium ion battery (LIB) electrolytes. Liquid chromatographic techniques hyphenated to ion trap time-of-flight mass spectrometry reveal 122 different organophosphate (OP) and organofluorophosphate (OFP) species, the majority of which are not reported in the literature so far. The application of hydrophilic interaction liquid chromatography and reversed-phase chromatography enables the investigation of the acidic as well as nonacidic spectrum of aging products. Furthermore, the generation of high structure certainty by consideration of (i) mass accuracy of the precursor ions and subsequent MS2/3 fragments, (ii) fragment intensity distribution in the mass spectra, and (iii) retention times in hydrophilic interaction liquid chromatography (HILIC) and reversed-phase (RP) separation allows a target analysis of further work in the LIB electrolyte context. In an ethyl methyl carbonate-based battery electrolyte, 82 OP compounds, 27 OFPs, and 13 cyclic O(F)Ps are identified. Additionally, the formation of 8-membered organo(fluoro)phosphate rings in lithium ion battery electrolytes is reported for the first time. Since the high toxic potential of organo(fluoro)phosphates has emerged interest in safety assessments of electrolytes, the knowledge of possibly formed substances supports further quantification approaches and toxicological assessments compared to nontarget investigations.

A new HILIC-ICP-SF-MS method for the quantification of organo(fluoro)phosphates as decomposition products of lithium ion battery electrolytes.

The lithium ion battery (LIB) is the most popular choice for powering consumer electronics, grid storage and electric vehicles. Decomposition reactions in LIBs, leading to so-called aging, are the main reason for loss of capacity and power and will affect LIB safety. Organo(fluoro)phosphates (O(F)Ps) as decomposition products of LIB electrolytes have been identified in several studies in the literature but quantitative data of O(F)Ps in LIBs are only scarcely available. In terms of toxicity, this substance class is highly relevant as it shows structural similarities to chemical warfare agents. Thus, approaches that can deliver quantitative data are in need. In this study, acidic O(F)Ps were quantified with an inductively coupled plasma-sector field-mass spectrometer (ICP-SF-MS) after separation of species with hydrophilic interaction liquid chromatography (HILIC). The formation of OFPs exceeds the amount of non-fluorine containing OPs by a factor of up to 15. A total of 16 different O(F)P compounds could successfully be quantified. Organic mass spectrometry was used for the assignment of quantitative data.