This thesis focuses on the development of oxidatively stable cathode and electrolyte materials for sodium-based battery systems. This is primarily achieved through the use of solid-state nuclear magnetic resonance (ssNMR) and pulsed-field gradient (PFG) NMR spectroscopy.
ssNMR is used to diagnose the primarily failure mode of the NaOB. It is found through a combined 23Na and 19F study that the main discharge product of the cell, NaO2, oxidizes both the carbon and polyvinylidene fluoride (PVDF) binder of the cathode to produce parasitic Na2CO3 and NaF. In a subsequent study, Ti4O7-coated carbon paper cathodes are implemented in an attempt to stabilize NaO2. The 23Na triple quantum magic angle spinning (3QMAS) and 1H to 23Na dipolar heteronuclear multiple quantum correlation (23Na{1H} D-HMQC) experiments are used to diagnose the failure modes of carbon-coated, and Ti4O7-coated cathodes. It is found that electrochemically formed NaO2 is significantly more stable in Ti4O7-coated cathodes, leading to longer lifetime NaOBs.
Oxidatively stable electrolyte materials are also examined. Lithium and sodium bis(trifluoromethansulfonyl)imide (TFSI) in adiponitrile (ADN) electrolytes exhibit extreme oxidative resistance, but are unusable in modern cells due to Al corrosion by TFSI, and spontaneous ADN degradation by Li and Na metal. PFG NMR is used to investigate the transport properties of LiTFSI in ADN as a function of LiTFSI concentration. By measuring the diffusion coefficient of Li+ and TFSI as a function of diffusion time (Δ), diffusional behaviour is encoded as a function of length scale to study the short- and long-range solution structure of the electrolyte. It is found that at high concentrations, LiTFSI in ADN transports Li+ primarily through an ion-hopping mechanism, in contrast to the typical vehicular mechanism observed at low concentrations. This suggests significant structural changes in solution at high concentrations.
The NaTFSI in ADN analogue is examined for its electrochemical properties in Na-ion and Na-O2 batteries. It is found that the oxidative resistance of ADN to Na metal is significantly increased at high concentrations, leading to reversible Na deposition and dissolution in cyclic voltammetry (CV) experiments. Linear sweep voltammetry (LSV) and chronoamperometry (CA) experiments on Al current collectors show that Al corrosion by TFSI is similarly suppressed at high concentration. This culminates in high concentration NaTFSI in ADN being able to reversibly intercalate Na3V2(PO4)2F3 (NVPF) cathodes in SIB half-cells for multiple cycles.
The knowledge gained from exploring oxidatively stable cathode and electrolyte materials can be used in tandem for the development of a longer lifetime, more oxidatively stable, NaOB in the future. / Thesis / Doctor of Philosophy (PhD) / The continued development of rechargeable batteries is paramount in reducing the world’s reliance on fossil fuels, as they allow for the storage of electrical energy produced by renewable sources. This work primarily examines sodium-based batteries systems, such as the sodium-oxygen battery (NaOB) and sodium-ion battery (SIB), which are possible alternatives to the currently used lithium-ion battery (LIB) system.
In order to produce energy, NaOBs produce sodium superoxide (NaO2) during the discharge process, which is formed on the carbon cathode. However, NaO2 is inherently unstable to carbon materials, causing degradation of the battery overtime. Ti4O7 is investigated as a stable coating material in NaOBs, used to coat the carbon cathode to make the system more stable to NaO2 degradation. The degradation processes in NaOBs are characterized by solid state nuclear magnetic resonance (ssNMR) spectroscopy, which uses strong superconducting magnets to probe the magnetic properties of, and consequently identify, the chemical species formed within the battery. It is found that the addition of the Ti4O7 coating inhibits NaO2 degradation, producing longer lifetime NaOBs.
Subsequently, both Li-bis(trifluoromethansulfonyl)imide (LiTFSI), and NaTFSI, in adiponitrile (ADN) electrolytes are examined for their use in LIBs and SIBs, respectively. Electrolytes facilitate stable ion transport within the cell, and ADN electrolytes specifically allow for the use of higher voltage cathode materials, which can result in a higher energy density battery. The transport properties of LiTFSI in ADN electrolytes are studied by a pulsed-field gradient (PFG) NMR technique, that allows for the measurement of the rate of ion transport in the electrolyte. It is found that the mechanism of ion transport significantly depends on electrolyte concentration, which suggests significant changes to the electrolyte solution structure at high concentration.
The electrochemical ramifications of this are studied for the NaTFSI in ADN electrolyte in SIBs. It is found that the electrolyte becomes substantially more stable at high concentrations, leading to more favourable charging and discharging behaviours when tested in SIBs.
The work presented in this thesis illustrates the development of more stable, longer lifetime, batteries over a number of cell chemistries, using a variety of NMR and electrochemical characterization techniques.
| Identifer | oai:union.ndltd.org:mcmaster.ca/oai:macsphere.mcmaster.ca:11375/28151 |
| Date | January 2022 |
| Creators | Franko, Christopher J. |
| Contributors | Goward, Gillian, Chemistry |
| Source Sets | McMaster University |
| Language | English |
| Detected Language | English |
| Type | Thesis |
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