The hydrolysis products fluoride (F(-)), monofluorophosphate (HPO(3)F(-)), phosphate (HPO(4)(2-)) and difluorophosphate (PO(2)F(2)(-)) were found and were unambiguously identified by means of standards or electrospray ionization mass spectrometry (ESI-MS).
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The software used for controlling the IC was the 792 Basic IC 1.0 (Metrohm). While peak 1 was identified as fluoride (see Section 3.1), PF 6 (4), difluorophosphate. Fricke MW, Zeller M, Sun H, Lai VW, Cullen WR, Shoemaker JA, Witkowski MR, Creed JT. However, using LiPF 6 is disadvantageous due to its thermal instability as observed by differential scanning calorimetry (DSC) and adiabatic calorimetry (ARC) . eCollection 2019 Apr 9. which is followed by the reaction between the formed POF 2 (OH) and water under formation of monofluorophosphoric acid (POF(OH) 2 ): The proposed decomposition products including structural formula and molecular weight are depicted in . Kkl JM, Aln RJ, Isoaho JP, Matilainen RB. The electrolytes of conventional LIBs typically consist of a mixture of linear and cyclic organic carbonates and lithium hexafluorophosphate (LiPF 6 ) as electrolyte salt due to its high conductivity, SEI forming ability and aluminum (cathode current collector) protection.
The site is secure. Separation of the hydrolysis products of LiPF 6 was carried out using an anion separation column model Metrosep Supp 4 (Metrohm, Herisau, Switzerland) with the following dimensions: 250 mm length 4.0 mm i.d., 9 mm particle size. 
To browse Academia.edu and the wider internet faster and more securely, please take a few seconds toupgrade your browser. Compared with , the peaks hold the same retention times. They suggested that POF 3 further decomposes in presence of water to difluorophosphoric acid (POF 2 (OH)). eCollection 2021. 
Unable to load your collection due to an error, Unable to load your delegates due to an error. Investigations and identification of decomposition products with a new method in an LIB electrolyte. Notice that in order to avoid peak overlapping the sample was additionally tenfold diluted. 
PF 6 and the formed main decomposition products F , PO 2 F 2 and HPO 3 F were separated by ion chromatography (IC) and detected by electrospray ionization mass spectrometry (ESI-MS). of 0.25 mm. Before In , the chromatogram of the commercially available electrolyte (without water addition) stored at 35 C for the same time (4 weeks) is shown. The API2000 and QTRAP3200 were controlled by the Analyst 1.4.1 and 1.5.1 softwares respectively, (both from Applied Biosystems). Chromatographic separation and identification of products from the reaction of dimethylarsinic acid with hydrogen sulfide. A preliminary reaction cycle was proposed for the thermal decomposition of the investigated system. Gu S, Wang J, Kaspar RB, Fang Q, Zhang B, Bryan Coughlin E, Yan Y. Sci Rep. 2015 Jun 29;5:11668. doi: 10.1038/srep11668. Ion chromatographic determination of hydrolysis products of hexafluorophosphate salts in aqueous solution, The influence of different conducting salts on the metal dissolution and capacity fading of NCM cathode material, Role of PF 6 in the radiolytical and electrochemical degradation of propylene carbonate solutions, Aging of Li2FeSiO4 cathode material in fluorine containing organic electrolytes for lithium-ion batteries, Investigations on the electrochemical performance and thermal stability of two new lithium electrolyte salts in comparison to LiPF6, APPLICATIONS OF IONIC LIQUIDS IN SCIENCE AND TECHNOLOGY, Dendrite-free Li deposition using trace-amounts of water as an electrolyte additive, Aging stability of Li2FeSiO4 polymorphs in LiPF6 containing organic electrolyte for lithium-ion batteries, Extraction of lithium-ion battery electrolytes with liquid and supercritical carbon dioxide and additional solvents, Is 3-methyl-2-oxazolidinone a suitable solvent for lithium-ion batteries, Batterie Litio-ione: sulla catena degli eventi termici che pu condurre a esplosione ed incendio MINISTERO DELLO SVILUPPO ECONOMICO, LiBOB as Salt for Lithium-Ion Batteries:A Possible Solution for High Temperature Operation, Physicochemical and electrochemical investigations of the ionic liquid N-butyl -N-methyl-pyrrolidinium 4,5-dicyano-2-(trifluoromethyl) imidazole, Studies on ionic liquidbased corn starch biopolymer electrolytes coupling with high ionic transport num, Studies on ionic liquid-based corn starch biopolymer electrolytes coupling with high ionic transport number, Anion Effects on Solid Polymer Electrolytes Containing Sulfur Based Ionic Liquid for Lithium Batteries, Solid polymer electrolytes with sulfur based ionic liquid for lithium batteries, Block Copolymer Electrolyte with Sulfur Based Ionic Liquid for Lithium Batteries, A conductivity study of preferential solvation of lithium ion in acetonitrile-dimethyl sulfoxide mixtures, Syntheses of a wide variety of new aryl based perfluorosulfonimide lithium salt. official website and that any information you provide is encrypted Four peaks were detected with the following retention time: 1 3.45 min, 2 4.25 min, 3 7.37 min and 4 10.86 min. As a further step towards the understanding of aging phenomena in LIBs, the ion chromatography (IC) method presented in this work was developed to separate the decomposition products of LiPF 6 and other compounds formed during the thermal aging of a commercially available electrolyte system EC/DEC (3:7 w/w). Three baselineseparated peaks (peaks 2, 3 and 4) were detected. Since the carbonates release CO 2 during the aging process, the resulting alcohols act as an additional reaction source. The compounds were analyzed first with conductivity and afterwards with ESI-MS detection. Baseline separation was obtained for all of the decomposition products. Stenzel YP, Henschel J, Winter M, Nowak S. RSC Adv. In , the chromatogram (conductivity detection) of a commercially available battery electrolyte containing LiPF 6 is presented. Here, several new decomposition products appear due to the temperature influence on the system. 2015 Aug 28;1409:201-9. doi: 10.1016/j.chroma.2015.07.054. 2019 Apr 11;9(20):11413-11419. doi: 10.1039/c9ra01291e. Copyright 2011 Elsevier B.V. All rights reserved. While LiPF 6 completely dissociates in water, ion pairs often occur in organic solvents, which in turn changes the reaction path . 2008 May 9;1190(1-2):150-6. doi: 10.1016/j.chroma.2008.02.096. Qualitative analysis of LiPF 6 based on IC with a conductivity detector, IC/ESI-MS and IC/ICP-OES was carried out to identify its decomposition products in aqueous solution. mobile phones or notebooks . Academia.edu no longer supports Internet Explorer. Complementary analyses for identification purposes were therefore performed by IC/ICP-OES and IC/ESI-MS, which results are presented in the following. Plakhotnyk et al. 2021 Sep 1;9:727382. doi: 10.3389/fchem.2021.727382. The .gov means its official. of 0.25 mm. A Basic IC 792 ion chromatograph and an 881 Compact IC pro Anion MCS from Metrohm AG (Herisau, Switzerland) were used for IC measurements. Preparation of Furfural From Xylose Catalyzed by Diimidazole Hexafluorophosphate in Microwave. However, considering the hydrolysis rate, which is described in literature as slow, peak 4 could belong to hexafluorophosphate . The https:// ensures that you are connecting to the Proposed reaction cycle for the electrolyte system. The corresponding chromatograms recorded with ESI-MS in single ion mode (SIM) are presented in . For IC/ESI-MS measurements, an API2000 and a QTRAP3200 mass spectrometer from Applied Biosystems (Darmstadt, Germany) were used with an electrospray ionization source. In this work, hydrolysis of three different hexafluorophosphate salts in purified water was investigated. All chemicals were of the highest quality available. Chem Res Toxicol. (2) and monofluorophosphate were detected as well. Purified water (18.2 MU 1 cm 1 , TOC <4 ppb, Milli-Q Advantage A10, Millipore GmbH, Schwalbach, Germany) was used for all experiments. Electrochemical performances of the related polymer electrolytes, On the limited performances of sulfone electrolytes towards the LiNi0.4Mn1.6O4 spinel, Stability of Ionic Liquids in Application Conditions, Preparation of microporous Cellulose/Poly(vinylidene fluoride- hexafluoropropylene) membrane for lithium ion batteries by phase inversion method, Syntheses of a wide family of new aryl based perfluorosulfonimide lithium salts. Furthermore, studies have shown that difluorophosphate (F 2 PO 2 ) can be formed by the hydrolysis reaction [16e19]. For future work, a gradient step should be applied instead of the isocratic step, since some of the new compounds, especially those detected at peaks 2 and 4 in , could not be baseline separated. shows the chromatogram with conductivity detection of the above-mentioned LiPF 6 aqueous solution stored for four weeks at room temperature. Careers. Lithium ion batteries (LIBs) are one of the most important energy sources for portable electronic devices, e.g. J Chromatogr A. The Role of Sub- and Supercritical CO2 as "Processing Solvent" for the Recycling and Sample Preparation of Lithium Ion Battery Electrolytes.
An official website of the United States government. IC/ESI-MS was used to identify the compounds separated by IC, as described earlier. The injection volume was 20 mL. 2003;17(14):1517-27. doi: 10.1002/rcm.1030. Besides its dissociation to Li and PF 6 , LiPF 6 is also in equilibrium with lithium fluoride (LiF) and phosphorus pentafluoride (PF 5 ) in aqueous solution. Ion chromatography electrospray ionization mass spectrometry method development and investigation of lithium hexafluorophosphate-based organic electrolytes and their thermal decomposition products. column and 2.5 mM KHCO(3)-2.5 mM K(2)CO(3) eluent was established. This is important for the quantification of the decomposition products using IC/ICP-OES or IC/ICP-MS since there are no commercially available standards available today. For the detection and identification of the formed decomposition products, an IC method using IonPac AS14A 250 mm 4.0 mm i.d. 8600 Rockville Pike
For the hyphenation of IC with ICP-OES or ESI-MS a solution of 1 mmol L 1 LiPF 6 in water was prepared, which was stored at room temperature. 2005 Dec;18(12):1821-9. doi: 10.1021/tx050227d. Epub 2008 Mar 6. The IC system was coupled to the ICP-OES using PEEK tubing with an inner diameter (i.d.) Rapid Commun Mass Spectrom. Difluorophosphoric acid 2 was detected with m/z 100.9 at t R 4.25 min, monofluorophosphoric acid 3 with m/ z 99.0 at t R 7.36 min and hexafluorophosphate 4 with m/ z 145.0 at t R 11.01 min.
Bethesda, MD 20894, Web Policies A non-spiked electrolyte sample was stored at 35 C for the thermal aging investigations to show the different impact of temperature in contrast to water content. However, when packed in large batteries, such as those required for EV and HEV applications, LIBs are prone to accelerated aging and low safeness. Additionally peak (2) revealed a contribution from FPO 3 C 2 H 5 while peak (4) was generated by the following decomposition products FPO 4 C 4 H 10 , FPO 5 C 6 H 14 and FPO 6 C 8 H 18, which were all detected as single charged anions. PMC According to these studies and the proposed hydrolysis reaction scheme, it is expected that the peaks might consist of difluorophosphoric acid and monofluorophosphoric acid. This results support for very different decomposition rates resulting from the lower dielectric constant of the electrolyte . Investigations on the thermal stability of LiPF 6 in presence of water. FOIA A new HILIC-ICP-SF-MS method for the quantification of organo(fluoro)phosphates as decomposition products of lithium ion battery electrolytes. Epub 2014 Jun 7. ICP-OES parameters are presented in . Inductively coupled plasma optical emission spectroscopy (ICP-OES) on the phosphorous trace supported the results obtained by ESI-MS. The conductivity detector was also used for comparison. During the hydrolysis investigations, four degradation peaks were separated by IC and detected with conductivity detection. Both systems consisted of a suppressor for chemical suppression, which acts as a cation exchanger to remove cations and replace them with an H so that the background noise is lowered to 1 mS and a conductivity detector. A solution of LiPF 6 in water (10 mmol L 1 ) was analyzed by IC with conductivity detection. The separation efficiency of IC allowed baseline separation of all investigated analytes within less than 13 min. Further peaks in the chromatogram could not identified by IC using conductivity detection. and transmitted securely. The decomposition products were identified by their m/z ratio. For isocratic separations, the mobile phase consisted of a solution of 2.0 mmol L 1 sodium bicarbonate and 4.2 mmol L 1 sodium carbonate in a mixture of 30% acetonitrile (AcN) and 70% water (v/v). Novel methods based on hyphenated analytical techniques for the analysis of LiPF 6 commercially available battery electrolytes are presented. Federal government websites often end in .gov or .mil. A novel method for the analysis of LiPF 6 and battery electrolytes was presented. Sorry, preview is currently unavailable. In a previous work it was shown the usefulness of ion chromatography to investigate the decomposition products of LiPF 6 . Bookshelf Additionally, it was shown that temperature influence is more important than water impurities regarding the aging process of the electrolyte. Determination of low-molecular-mass aliphatic carboxylic acids and inorganic anions from kraft black liquors by ion chromatography. You can download the paper by clicking the button above. sharing sensitive information, make sure youre on a federal A commercially available battery electrolyte containing 1 mol L 1 LiPF 6 with EC/DEC (3:7 w/w) was spiked with 600 ppm (3.3 10 2 mol L 1 ) of purified water. Clipboard, Search History, and several other advanced features are temporarily unavailable. Hence, peaks 2, 3 and 4 are phosphorus compounds. Additionally, due to the high hygroscopicity of LiPF 6 , battery grade electrolytes contain about 25 ppm water , which favors spontaneous decomposition reactions since LiPF 6 is decomposed in the presence of water . Molecules. The SPECTRO ARCOS was controlled by the Smart Analyzer Vision 4.0 software (SPECTRO). Kraft V, Grtzke M, Weber W, Menzel J, Wiemers-Meyer S, Winter M, Nowak S. J Chromatogr A. government site. Enter the email address you signed up with and we'll email you a reset link. Huang T, Yuan K, Nie XL, Chen J, Zhang HX, Chen JZ, Xiong WM. HHS Vulnerability Disclosure, Help By interaction between the strong Lewis acid PF 5 and water, phosphorus oxyfluoride (POF 3 ) is formed . Afterwards the electrolyte was stored at room temperature. Acetonitrile (AcN, HPLC grade) was obtained from VWR International GmbH (Darmstadt, Germany). Aqueous samples of lithium hexafluorophosphate (LiPF(6)), sodium hexafluorophosphate (NaPF(6)) and potassium hexafluorophosphate (KPF(6)) were prepared and stored for different times. A lithium hexafluorophosphate sample (aqueous solution), which was stored for four weeks was analyzed by IC. already studied the decomposition of LiPF 6 in the water containing propylene carbonateedimethyl carbonate system by F and 31 P NMR spectroscopy . Anhydrous sodium carbonate (Na 2 CO 3 ), sodium bicarbonate (NaHCO 3 ) and battery electrolyte were purchased from Merck KGaA (Darmstadt, Germany). Based on Karl Fischer measurements, the electrolyte contained 25 ppm of water. The PEEK tubing was directly connected to a MiraMist Teflon nebulizer (Burgener, Mississauga, Ontario, Canada) and a cyclonic spray chamber, which was operated at room temperature. ESI-MS parameters are presented in . For identification of the detected decomposition products, the IC was connected to ESI-MS. Accessibility Ion chromatography (IC) with UV as well as non-suppressed and suppressed conductivity detection was used for the analysis of the reaction products. Subsequently, the same commercially available electrolyte system was analyzed to prove the usefulness of the proposed method to investigate the influence of the thermal aging in lithiumion batteries. However, in this work UVevis detection was replaced with conductivity detection and for unknown compounds, electrospray ionization mass spectrometry (ESI-MS) and inductively coupled plasma optical emission spectroscopy (ICP-OES) were complementary used for detection and identification purposes. In the ESI-MS chromatogram of the aqueous LiPF 6 sample is shown. Furthermore, it was demonstrated that the determination and identification of decomposition products in commercial battery electrolyte solutions are possible using the newly developed methods. Permethyl Cobaltocenium (Cp*2Co+) as an Ultra-Stable Cation for Polymer Hydroxide-Exchange Membranes. A Metrosep Supp 4/5 guard (Metrohm) was used to avoid contamination of the analytical column. All the compounds which were found in the water spiked sample were also present in this chromatogram: (1), fluoride, (3), difluorophosphate (5), PF and monofluorophosphate. The sample was spiked with 600 ppm of water and stored at room temperature for several weeks. Besides hexafluorophosphate, four other anionic species were detected in fresh and matured aqueous solutions. By comparison with a standard, peak 1 was identified as fluoride.
Additionally, the relatively low amount of water present in the commercial electrolyte (up to 25 ppm) is certainly not enough for reactions (3)e(5) (see above) to proceed since water is stoichiometrically involved in these reactions.
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