Encapsulation of flame retardants for lithium-ion battery safety
- Authors: Ntombela, Nompilo Princess
- Date: 2022-04
- Subjects: Port Elizabeth (South Africa) , Eastern Cape (South Africa) , South Africa
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/55412 , vital:51993
- Description: Lithium-ion technology takes the lead in electric mobility systems, resulting in an increase in the global demand for Li-ion batteries; however, these batteries are associated with numerous safety concerns. Additionally, there are high costs, high energy and power issues which are some of its key limitations. Research efforts are focused on overcoming these obstacles, with different approaches being explored, such as the investigation of more stable salts, modification of active materials and organic solvents, and the use of electrolyte additives. This study focused specifically on electrolyte additives since the electrolyte is one of the most unstable components of the battery. The electrolyte’s decomposition is one of the reactions that occur inside a battery, which may occur due to overcharging or due to an internal short circuit, amongst others. The electrolyte’s decomposition occurs at the early stages of the thermal runaway process and forms part of the reactions that lead to fires and explosions. Thus, this research aims to develop suitable electrolyte additives to improve the safety aspects of Li-ion batteries. Flame retardant additives show great promise in reducing the flammability of the electrolyte in Li-ion batteries, since they serve to suppress the chemical reactions associated with battery ignition. They retard the fires by scavenging the active radical species formed during the decomposition reaction. In this study, the use of flame retardants was investigated. Flame retardant additives have shown to have flame impeding properties inside a battery; however, their direct addition to the electrolyte tends to cause adverse effects on the ionic conductivity and electrochemical performance of the cells. This study investigated an alternative option - the option to microencapsulate such additives into a neutral compound to ensure that the flame retardant has minimal/no effect on the performance of the battery. This investigation looked at tris(2-butoxyethyl) phosphate (TBP) and bis(2,2,2-trifluoroethyl) methylphosphonate (BFP) as flame retardant additives for the electrolyte. The TBP and BFP flame retardants were microencapsulated in poly(urea formaldehyde) (PUF) coating material via in situ polymerization method. The capsules were characterized using various analytical techniques - to prove it was successfully encapsulated. Electrochemical studies were further done on the capsules and neat flame retardants inside a coin cell. Self-extinguishing time (SET), which is the flammability test, proved that the additives have flame retarding abilities. Opto-digital microscopy (DSX) and scanning electron microscopy (SEM) did confirm the spherical shape of the microcapsules, where SEM also showed the smooth outer layer of the microcapsules and its hollow inner side. Fourier transform infrared spectroscopy (FTIR) proved the presence of the TBP and BFP inside the PUF resin by showing that the chemical composition of microcapsules consisted of both the PUF and flame retardant additives. Simultaneous DSC-TGA (DST) was also performed which showed that the microcapsules were stable before 200 °C, which indicates it would not decompose before the thermal runaway events are occurring. TGA analysis did show that the microcapsules underwent multiple decomposition steps upon heating. Additionally, 31P nuclear magnetic resonance (NMR) was used to quantify the amount of flame retardants additives encapsulated inside PUF shell, and also confirmed the stability of the microcapsules for one month in the electrolyte and at temperatures up to 200 °C. The ionic conductivity was vastly decreased when the flame retardants were added directly to the electrolyte. However, adding the flame retardants in a form of capsules had minimal effect on the ionic conductivity. The cycle capacities of the capsules were also improved when the capsules were added to the cell compared to that of neat flame retardants. The same effect was also noticed when doing Electrochemical Impedance Spectroscopy (EIS). This shows that microencapsulation improves the resistance of the cell caused by the flame retardant in comparison to when added directly to the electrolyte of the cell. , Thesis (MSC) -- Faculty of Science, School of Biomolecular and Chemical Sciences, 2022
- Full Text:
- Date Issued: 2022-04
- Authors: Ntombela, Nompilo Princess
- Date: 2022-04
- Subjects: Port Elizabeth (South Africa) , Eastern Cape (South Africa) , South Africa
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/55412 , vital:51993
- Description: Lithium-ion technology takes the lead in electric mobility systems, resulting in an increase in the global demand for Li-ion batteries; however, these batteries are associated with numerous safety concerns. Additionally, there are high costs, high energy and power issues which are some of its key limitations. Research efforts are focused on overcoming these obstacles, with different approaches being explored, such as the investigation of more stable salts, modification of active materials and organic solvents, and the use of electrolyte additives. This study focused specifically on electrolyte additives since the electrolyte is one of the most unstable components of the battery. The electrolyte’s decomposition is one of the reactions that occur inside a battery, which may occur due to overcharging or due to an internal short circuit, amongst others. The electrolyte’s decomposition occurs at the early stages of the thermal runaway process and forms part of the reactions that lead to fires and explosions. Thus, this research aims to develop suitable electrolyte additives to improve the safety aspects of Li-ion batteries. Flame retardant additives show great promise in reducing the flammability of the electrolyte in Li-ion batteries, since they serve to suppress the chemical reactions associated with battery ignition. They retard the fires by scavenging the active radical species formed during the decomposition reaction. In this study, the use of flame retardants was investigated. Flame retardant additives have shown to have flame impeding properties inside a battery; however, their direct addition to the electrolyte tends to cause adverse effects on the ionic conductivity and electrochemical performance of the cells. This study investigated an alternative option - the option to microencapsulate such additives into a neutral compound to ensure that the flame retardant has minimal/no effect on the performance of the battery. This investigation looked at tris(2-butoxyethyl) phosphate (TBP) and bis(2,2,2-trifluoroethyl) methylphosphonate (BFP) as flame retardant additives for the electrolyte. The TBP and BFP flame retardants were microencapsulated in poly(urea formaldehyde) (PUF) coating material via in situ polymerization method. The capsules were characterized using various analytical techniques - to prove it was successfully encapsulated. Electrochemical studies were further done on the capsules and neat flame retardants inside a coin cell. Self-extinguishing time (SET), which is the flammability test, proved that the additives have flame retarding abilities. Opto-digital microscopy (DSX) and scanning electron microscopy (SEM) did confirm the spherical shape of the microcapsules, where SEM also showed the smooth outer layer of the microcapsules and its hollow inner side. Fourier transform infrared spectroscopy (FTIR) proved the presence of the TBP and BFP inside the PUF resin by showing that the chemical composition of microcapsules consisted of both the PUF and flame retardant additives. Simultaneous DSC-TGA (DST) was also performed which showed that the microcapsules were stable before 200 °C, which indicates it would not decompose before the thermal runaway events are occurring. TGA analysis did show that the microcapsules underwent multiple decomposition steps upon heating. Additionally, 31P nuclear magnetic resonance (NMR) was used to quantify the amount of flame retardants additives encapsulated inside PUF shell, and also confirmed the stability of the microcapsules for one month in the electrolyte and at temperatures up to 200 °C. The ionic conductivity was vastly decreased when the flame retardants were added directly to the electrolyte. However, adding the flame retardants in a form of capsules had minimal effect on the ionic conductivity. The cycle capacities of the capsules were also improved when the capsules were added to the cell compared to that of neat flame retardants. The same effect was also noticed when doing Electrochemical Impedance Spectroscopy (EIS). This shows that microencapsulation improves the resistance of the cell caused by the flame retardant in comparison to when added directly to the electrolyte of the cell. , Thesis (MSC) -- Faculty of Science, School of Biomolecular and Chemical Sciences, 2022
- Full Text:
- Date Issued: 2022-04
A study of the airflow on the windward slope of a transverse dune in the Alexandria coastal dunefield
- Authors: Burkinshaw, Jennifer Ruth
- Date: 2021-04
- Subjects: Port Elizabeth (South Africa) , Eastern Cape (South Africa) , South Africa
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/52734 , vital:43883
- Description: Our understanding of the evolution of dune morphology has been hampered by a lack of empirical observations of airflow behaviour over dune forms. Sand dunes intrude into the atmospheric boundary layer and convergence of streamlines results in an acceleration of airflow up the windward slopes of dunes. This study examines the airflow structure and corresponding bedform development on the windward slope of a 7 m high transverse dune on the edge of the Alexandria coastal dunefield, Algoa Bay, South Africa. The Alexandria dunefield is subjected to a trimodal wind regime, consisting of the dominant south-westerly which blows all year round, summer easterlies and winter northwesterlies. The morphology of the study dune, Dune13, is controlled by the easterlies and north-westerlies, and reverses seasonally with respect to these two winds. Seven section lines 30 m apart and normal to the dune crest were surveyed regularly over the period of a year to monitor the reversal process. Three detailed topographic surveys were also done during this period. Airflow behaviour was monitored during the year. Wind speed profiles on the windward slope of the dune were measured using 4 to 5 vertical arrays of anemometers positioned from the base of the dune to the crest on a 1 selected section line. Usually 4 to 5 anemometers were deployed in each vertical array, from a height of 6 to 10 cm above the surface, up to a height of 150 cm above the surface. Initially 8 microanemometers were available; ultimately 28 anemometers were run simultaneously. An independent weather station at an elevation of 6 m recorded the unaccelerated flow. Local gradient measurements and erosion and deposition rates were recorded along selected section lines. Strong summer easterly winds (14 m/sec at 1.4 m above the dune crest) were measured on a dune slope in the process of being transformed from a slipface to a stoss slope. The following winter, light north-westerly winds (typically B m/sec at 1.6 m above the dune crest) were measured on the new windward slope already reversed by the prevailing winter wind. Airflow data confirm the compression of airflow against the windward slope resulting in a non-logarithmic wind speed profile. Compression results in an increased shear velocity within 30 cm of the dune surface, and the dune slope is eroded. Higher up in the wind speed profile, shear velocity decreases to 0.1 m/sec. It is not known at what height the wind speed profile recovers from the intrusion of the dune into the boundary layer. High values of shear velocity (1.6 m/sec) above the rounded crestal area of the dune record the recovery of the wind speed profile from flow divergence, which is a response to the rapid reduction of dune gradient and is accompanied by deposition of sand in this region. 2 The erosion pin data act as a simple and sensitive test for changes in gradient, reflecting the dune's response to changes in the airflow regime. The shape of the dune plays a major role in determining the extent of the compression and the distribution of shear velocity up the slope. Increased shear velocity is experienced on that part of the slope which is nonaerodynamic with respect to the prevailing wind. Under unidirectional conditions, feedback between flow and form results ultimately in a slope with a curvature such that shear velocity increases systematically upslope. The survey data and erosion pin data record the reversal process as the dune achieves a new steady state during each wind season. The existence of a non-logarithmic wind speed profile makes it difficult to know what relevant measure of shear velocity is to be used in sand transport equations. Future work should include wind speed measurements within 10 cm of the surface. An ideal study modelling aeolian bedform development would utilise wind tunnel measurements, combined with field measurements such as obtained in this study, for comparison with numerical modelling. The study needs to be extended to 3-dimensional airflow measurements. , Thesis (MSc) -- Faculty of Science, School of Environmental Sciences, 2021
- Full Text:
- Date Issued: 2021-04
- Authors: Burkinshaw, Jennifer Ruth
- Date: 2021-04
- Subjects: Port Elizabeth (South Africa) , Eastern Cape (South Africa) , South Africa
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/52734 , vital:43883
- Description: Our understanding of the evolution of dune morphology has been hampered by a lack of empirical observations of airflow behaviour over dune forms. Sand dunes intrude into the atmospheric boundary layer and convergence of streamlines results in an acceleration of airflow up the windward slopes of dunes. This study examines the airflow structure and corresponding bedform development on the windward slope of a 7 m high transverse dune on the edge of the Alexandria coastal dunefield, Algoa Bay, South Africa. The Alexandria dunefield is subjected to a trimodal wind regime, consisting of the dominant south-westerly which blows all year round, summer easterlies and winter northwesterlies. The morphology of the study dune, Dune13, is controlled by the easterlies and north-westerlies, and reverses seasonally with respect to these two winds. Seven section lines 30 m apart and normal to the dune crest were surveyed regularly over the period of a year to monitor the reversal process. Three detailed topographic surveys were also done during this period. Airflow behaviour was monitored during the year. Wind speed profiles on the windward slope of the dune were measured using 4 to 5 vertical arrays of anemometers positioned from the base of the dune to the crest on a 1 selected section line. Usually 4 to 5 anemometers were deployed in each vertical array, from a height of 6 to 10 cm above the surface, up to a height of 150 cm above the surface. Initially 8 microanemometers were available; ultimately 28 anemometers were run simultaneously. An independent weather station at an elevation of 6 m recorded the unaccelerated flow. Local gradient measurements and erosion and deposition rates were recorded along selected section lines. Strong summer easterly winds (14 m/sec at 1.4 m above the dune crest) were measured on a dune slope in the process of being transformed from a slipface to a stoss slope. The following winter, light north-westerly winds (typically B m/sec at 1.6 m above the dune crest) were measured on the new windward slope already reversed by the prevailing winter wind. Airflow data confirm the compression of airflow against the windward slope resulting in a non-logarithmic wind speed profile. Compression results in an increased shear velocity within 30 cm of the dune surface, and the dune slope is eroded. Higher up in the wind speed profile, shear velocity decreases to 0.1 m/sec. It is not known at what height the wind speed profile recovers from the intrusion of the dune into the boundary layer. High values of shear velocity (1.6 m/sec) above the rounded crestal area of the dune record the recovery of the wind speed profile from flow divergence, which is a response to the rapid reduction of dune gradient and is accompanied by deposition of sand in this region. 2 The erosion pin data act as a simple and sensitive test for changes in gradient, reflecting the dune's response to changes in the airflow regime. The shape of the dune plays a major role in determining the extent of the compression and the distribution of shear velocity up the slope. Increased shear velocity is experienced on that part of the slope which is nonaerodynamic with respect to the prevailing wind. Under unidirectional conditions, feedback between flow and form results ultimately in a slope with a curvature such that shear velocity increases systematically upslope. The survey data and erosion pin data record the reversal process as the dune achieves a new steady state during each wind season. The existence of a non-logarithmic wind speed profile makes it difficult to know what relevant measure of shear velocity is to be used in sand transport equations. Future work should include wind speed measurements within 10 cm of the surface. An ideal study modelling aeolian bedform development would utilise wind tunnel measurements, combined with field measurements such as obtained in this study, for comparison with numerical modelling. The study needs to be extended to 3-dimensional airflow measurements. , Thesis (MSc) -- Faculty of Science, School of Environmental Sciences, 2021
- Full Text:
- Date Issued: 2021-04
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