Vadim Kraft

Ion chromatography electrospray ionization mass spectrometry method development and investigation of lithium hexafluorophosphate-based organic electrolytes and their thermal decomposition products

A method based on the coupling of ion chromatography (IC) and electrospray ionization mass spectrometry (ESI-MS) for the separation and determination of thermal decomposition products of LiPF6-based organic electrolytes is presented. The utilized electrolytes, LP30 and LP50, are commercially available and consist of 1mol/l LiPF6 dissolved in ethylene carbonate/dimethyl carbonate and ethylene carbonate/ethyl methyl carbonate, respectively. For the separation method development three ion chromatographic columns with different capacity and stationary phase were used and compared. Besides the known hydrolysis products of lithium hexafluorophosphate, several new organophosphates were separated and identified with the developed IC-ESI-MS method during aging investigations of the electrolytes. The chemical structures were elucidated with IC-ESI-MS/MS.

Qualitative and quantitative investigation of organophosphates in an electrochemically and thermally treated lithium hexafluorophosphate- based lithium ion battery electrolyte by a developed liquid chromatography-tandem quadrupole mass spectrometry method†

The presented work was focused on the development of a new liquid chromatography-tandem quadrupole mass spectrometry method (LC-MS/MS) for the identification and quantification of organophosphates in lithium hexafluorophosphate (LiPF6)-based lithium ion battery electrolytes. The investigated electrolyte consists of 1 M LiPF6 dissolved in ethylene carbonate/ethyl methyl carbonate (50/50, wt%) and was treated electrochemically and thermally. For the electrochemical experiments, the cut-off potential in the half cells was held at 5.5 V for 72 h. The thermal degradation experiments were performed in aluminum vials at 95 °C for a period of 13 days. In the first part of this work, an already established gas chromatography-mass spectrometry (GC-MS) method for identification of dimethyl fluorophosphates (DMFP) and diethyl fluorophosphate (DEFP) was applied. In the second part, the LC-MS/MS method including determination of characteristic transitions in a product ion scan was developed. The developed method was applied for the identification of various analytes in the decomposed electrolytes. In addition, a possible formation of ionic and non-ionic OPs based on findings of this work and our previous reports is presented. In the third and final part, a quantification study of DMFP and DEFP was performed with a newly developed LC-MS/MS method and compared with results obtained by GC-MS. In addition, trimethyl phosphate (TMP) and triethyl phosphate (TEP) were quantified. These studies included the investigation of the suppression effects caused by the sample matrix during the application of the LC-MS/MS method.

Identification of alkylated phosphates by gas chromatography–mass spectrometric investigations with different ionization principles of a thermally aged commercial lithium ion battery electrolyte

The thermal aging process of a commercial LiPF6 based lithium ion battery electrolyte has been investigated in view of the formation of volatile phosphorus-containing degradation products. Aging products were analyzed by GC-MS. Structure determination of the products was performed by support of chemical ionization MS in positive and negative modes. A fraction of the discovered compounds belongs to the group of fluorophosphates (phosphorofluoridates) which are in suspect of potential toxicity. This is well known for relative derivatives, e.g. diisopropyl fluorophosphate. Another fraction of the identified compounds belongs to the group of trialkyl phosphates. These compounds may provide a positive impact on the thermal and electrochemical performance of Li-based batteries as repeatedly described in the literature.

Two-dimensional ion chromatography for the separation of ionic organophosphates generated in thermally decomposed lithium hexafluorophosphate-based lithium ion battery electrolytes.

A two-dimensional ion chromatography (IC/IC) technique with heart-cutting mode for the separation of ionic organophosphates was developed. These analytes are generated during thermal degradation of three different commercially available Selectilyte™ lithium ion battery electrolytes. The composition of the investigated electrolytes is based on 1M lithium hexafluorophosphate (LiPF6) dissolved in ethylene carbonate/dimethyl carbonate (50:50wt%, LP30), ethylene carbonate/diethyl carbonate (50:50wt%, LP40) and ethylene carbonate/ethyl methyl carbonate (50:50wt%, LP50). The organophosphates were pre-separated from PF6(-) anion on the low capacity A Supp 4 column, which was eluted with a gradient step containing acetonitrile. The fraction containing analytes was retarded on a pre-concentration column and after that transferred to the high capacity columns, where the separation was performed isocratically. Different stationary phases and eluents were applied on the 2nd dimension for the investigation of retention times, whereas the highly promising results were obtained with a high capacitive A Supp 10 column. The organophosphates generated in LP30 and LP40 electrolytes could be separated by application of an aqueous NaOH eluent providing fast analysis time within 35min. For the separation of the organophosphates of LP50 electrolyte due to its complexity a NaOH eluent containing a mixture of methanol/H2O was necessary. In addition, the developed two dimensional IC method was hyphenated to an inductively coupled plasma mass spectrometer (ICP-MS) using aqueous NaOH without organic modifiers. This proof of principle measurement was carried out for future quantitative investigation regarding the concentration of the ionic organophosphates. Furthermore, the chemical stability of several ionic organophosphates in water and acetonitrile at room temperature over a period of 10h was investigated. In both solvents no decomposition of the investigated analytes was observed and therefore water as solvent for dilution of samples was proved as suitable.

Study of decomposition products by gas chromatography-mass spectrometry and ion chromatography-electrospray ionization-mass spectrometry in thermally decomposed lithium hexafluorophosphate-based lithium ion battery electrolytes

In this work, the thermal decomposition of a lithium ion battery electrolyte (1 M LiPF6 in ethylene carbonate/ethyl methyl carbonate, 50/50 wt%) with a focus on the formation of organophosphates was systematically studied. The quantification of non-ionic dimethyl fluorophosphate and diethyl fluorophosphate was performed with synthesized standards by gas chromatography-mass spectrometry. Due to absence of commercially available or synthesized standards for the monitoring of ionic methyl fluorophosphate, ethyl fluorophosphate and ethylene phosphate a method working with ion chromatography-electrospray ionization-mass spectrometry was developed, where dibutyl phosphate was used as an internal standard. In addition, an ion chromatography conductivity detection method with short analysis time for simultaneous determination and quantification of F−, PF6− and BF4− was developed. The formation and degradation of analytes was studied to show the dependence of different temperatures, electrolyte volumes and separator materials. The thermal aging experiments were carried out in gas-tight aluminum vials at 80 °C for three weeks. After the storage time, the samples were diluted with the appropriate analysis solvents and investigated with gas chromatography-mass spectrometry, ion chromatography and ion chromatography-electrospray ionization-mass spectrometry. Finally, the thermal degradation of the electrolyte at 85 °C after five days in aluminum and glass vials was studied.

Investigation of the Storage Behavior of Shredded Lithium‐Ion Batteries from Electric Vehicles for Recycling Purposes

Shredding of the cells is often the first step in lithium-ion battery (LIB) recycling. Thus, LiNi1/3 Mn1/3 Co1/3 O2 (NMC)/graphite lithium-ion cells from a field-tested electric vehicle were shredded and transferred to tinplate or plastic storage containers. The formation of hazardous compounds within, and being released from, these containers was monitored over 20 months. The tinplate cans underwent fast corrosion as a result of either residual charge in the active battery material, which could not fully be discharged because of contact loss to the current collector, or redox reactions between the tinplate surface and metal parts of the shredded material. The headspace compositions of the containers were investigated at room temperature and 150 °C using headspace-gas chromatography-mass spectrometry (HS-GC-MS). Samples of the waste material were also collected using microwave-assisted extraction and the extracts were analyzed over a period of 20 months using ion chromatography-electrospray ionization-mass spectrometry (IC-ESI-MS). LiPF6 was identified as a conducting salt, whereas dimethyl carbonate, ethyl methyl carbonate, and ethylene carbonate were the main solvent components. Cyclohexylbenzene was also detected, which is an additive for overcharge protection. Diethyl carbonate, fluoride, difluorophosphate and several ionic and non-ionic alkyl (fluoro)phosphates were also identified. Importantly, dimethyl fluorophosphate (DMFP) and diethyl fluorophosphate (DEFP) were quantified using HS-GC-MS through the use of an internal standard. DMFP, DEFP, and related compounds are known as chemical warfare agents, and the presence of these materials is of great interest. In the case of this study, these hazardous materials are present but in manageable low concentrations. Nonetheless, the presence of such compounds and their potential release during an accident that may occur during shredding or recycling of large amounts of LIB waste should be considered.

A fluoride-selective electrode (Fse) for the quantification of fluoride in lithium-ion battery (Lib) electrolytes

In this work, a fluoride-selective electrode (FSE) was applied with regard to the analysis of fluoride in lithium hexafluorophosphate-based lithium-ion battery (LIB) electrolytes. The influence of linear organic carbonate solvents dimethyl carbonate (DMC), ethyl methyl carbonate (EMC) and diethyl carbonate (DEC) which are used as co-solvents in battery electrolytes was investigated. The developed FSE method for the analysis of battery electrolytes was comprehensively validated in view of the (1) trueness and recovery rates (nominal vs. actual comparison; influence of different amounts of electrolytes on the performance of the electrode; recovery rates of defined differences in concentration), (2) precision (intra-day precision and inter-day precision), (3) selectivity (influence of the carbonate solvents on different fluoride concentrations; interferents) and (4) linearity and range. Statistical analysis was performed to evaluate the data and to characterize the reproducibility of the method. The determination of the commercially available LP30 (1 mol LiPF6 and ethylene carbonate/dimethyl carbonate (EC : DMC, 50 : 50 wt%)) electrolyte stored over 47 days and at 80 °C, by the FSE technique was compared to the fluoride analysis by ion chromatography (IC). While interferences in the IC method resulted in false-high concentrations, the FSE operated free from interferences, selective and specific. The validation of the method was successfully carried out and enables new areas of application.

Quantification of ionic organo(fluoro)phosphates in decomposed lithium battery electrolytes

A method for the separation, identification and quantification of the ionic decomposition products of LiPF6 based organic electrolytes was developed. It employed the simultaneous coupling of two-dimensional ion chromatography (2D IC) with electrospray-ionization mass spectrometry (ESI-MS) and with inductively coupled plasma-mass spectrometry (ICP-MS). The electrolyte under investigation was a commercially available electrolyte by BASF, consisting of 1 mol L−1 LiPF6 in a mixture of one linear and one cyclic organic carbonate (50 : 50 wt%). The quantification was based on the use of a structurally similar compound as calibration standard for the ICP-MS measurement, while the identification was carried out with ESI-MS. Several organo(fluoro)phosphate species were successfully separated and quantified. Since these species show a high structural similarity to the warfare agent sarin, their investigation is of special interest with regard to their potential toxicity. Additionally, a quantification study of an electrolyte extracted from a cycled lithium metal cell was carried out.