Extraction of lithium-ion battery electrolytes with liquid and supercritical carbon dioxide and additional solvents

Grützke, Martin; Mönnighoff, Xaver; Horsthemke, Fabian; Kraft, Vadim; Winter, Martin; Nowak, Sascha

doi:10.1039/c5ra04451k

Cited by 116 publications

(103 citation statements)

References 74 publications

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“…[8] Thus, this methodo ffers the possibility to reutilize nearly the all of the componentsf rom as pent LIB, which is of great benefitw ith regard to the recyclinge fficiency. The tendency to lower crystallinity with increasing carbon dioxide pressure was confirmed by Ramans pectroscopy.T oc onclude, despite smaller crystallinity size than non-extracted graphite particles, the electrolyte extraction using subcritical CO 2 is considered to be the best recycling method, as the recycled graphite shows the best electrochemical performance and the electrolyte is recovered by 90 %, including the conductive salt.…”

Section: Discussionmentioning

confidence: 99%

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Graphite Recycling from Spent Lithium‐Ion Batteries

et al. 2016

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The present work reports on challenges in utilization of spent lithium-ion batteries (LIBs)-an increasingly important aspect associated with a significantly rising demand for electric vehicles (EVs). In this context, the feasibility of anode recycling in combination with three different electrolyte extraction concepts is investigated. The first method is based on a thermal treatment of graphite without electrolyte recovery. The second method additionally utilizes a subcritical carbon-dioxide (subcritical CO )-assisted electrolyte extraction prior to thermal treatment. And the final investigated approach uses supercritical carbon dioxide (scCO ) as extractant, subsequently followed by the thermal treatment. It is demonstrated that the best performance of recycled graphite anodes can be achieved when electrolyte extraction is performed using subcritical CO . Comparative studies reveal that, in the best case, the electrochemical performance of recycled graphite exceeds the benchmark consisting of a newly synthesized graphite anode. As essential efforts towards electrolyte extraction and cathode recycling have been made in the past, the electrochemical behavior of recycled graphite, demonstrating the best performance, is investigated in combination with a recycled LiNi Co Mn O cathode.

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Section: Discussionmentioning

confidence: 99%

“…The applied electrolyte extraction methods have been published by Grützke et al [8,19] Full-cellinvestigations Therefore, the Speed SFE Basic extraction equipment (Applied Separations Inc.,A llentown, USA) was used.…”

Section: Electrolyte Removalmentioning

confidence: 99%

Graphite Recycling from Spent Lithium‐Ion Batteries

et al. 2016

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“…The analysis of OPs and electrolyte degradation in LIB electrolytes was already performed with different analytical techniques including nuclear magnetic resonance spectroscopy (NMR), 10,17 GC-MS [18][19][20] including supercritical extraction steps, 21,22 high resolution-electrospray ionization-mass spectrometry (HR-ESI-MS) [23][24][25] and low temperature plasma-ambient ionization-high resolution-mass spectrometry (LTP-HR-MS).…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2016

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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 (LiPF 6 )-based lithium ion battery electrolytes. The investigated electrolyte consists of 1 M LiPF 6 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.

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“…LIBs loose capacity over time owing to different aging phenomena . Various reports focused on method development for aging investigations of different cell components and the electrolyte are available in the literature . However, aging of LIBs is not only related to cycle life, but concerns also the formation of hazardous or corrosive compounds in the cell during aging.…”

Section: Introductionmentioning

confidence: 99%

“…[27] Various reports focusedo nm ethod development for aging investigationso fd ifferent cell components [28][29][30][31][32] and the electrolyte are availablei nt he literature. [12,16,[33][34][35][36][37][38][39][40][41][42][43][44][45][46][47][48][49][50][51][52] However, aging of LIBs is not only related to cyclel ife, but concerns also the formation of hazardous or corrosive compounds in the cell duringa ging. The formation of hydrofluorica cid, phosphoric acid, and alkyl fluorophosphate derivativesi sd emonstrated by different researchers.…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2015

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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.

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Extraction of lithium-ion battery electrolytes with liquid and supercritical carbon dioxide and additional solvents

Abstract: A flow-through method for the extraction of lithium-ion battery electrolytes with supercritical and liquid carbon dioxide under the addition of solvents has been developed and optimized to achieve quantitative extraction of the electrolyte from commercial 18 650 cells.

Cited by 116 publications

References 74 publications

Graphite Recycling from Spent Lithium‐Ion Batteries

Graphite Recycling from Spent Lithium‐Ion Batteries

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

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

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