- Title
- An investigation of the morphological and electrochemical properties of anode titanate materials used in li-ion batteries
- Creator
- Gelant, Charmaine
- Subject
- Electrodes
- Date Issued
- 2020
- Date
- 2020
- Type
- Thesis
- Type
- Masters
- Type
- MSc
- Identifier
- http://hdl.handle.net/10948/48346
- Identifier
- vital:40851
- Description
- The chemistry involved in the synthesis of lithium titanium oxide (Li4Ti5O12) for lithium ion battery applications is critical for understanding and optimizing the most cost-efficient manufacturing route. This study investigates the sol-gel synthesis technique of Li4Ti5O12 using triethanolamine (TEOA) as complexing agent by means of in-situ Powder X-ray Diffraction (PXRD). The influence of doping with various metals such as Al3+, Mg2+ , Co3+ and Ni2+ that were made as precursors was considered for comparison purposes due to literature showing improved electrochemical performance using the molecular formula of Li4Ti4.95M0.05O12. The in-situ PXRD technique was used to identify the phase changes that occurred in the thermal synthesis process from the sol-gel precursors to the final crystalline oxides. The materials’ decomposition mechanisms were characterized by thermal gravimetric analysis (TGA) as the precursors were gradually heated to obtain the final oxides. BET surface area analysis and scanning electron microscopy (SEM) were used in order to obtain a morphological understanding of the materials during the synthetic route at specific temperature regions. The in-situ studies have shown that the precursor materials are amorphous at room temperature to about 550 °C, after which the spinel and anatase formed, with relatively small crystallites and a large surface area. The study also showed that a crystalline intermediate phase formed at around 150-200 °C, which then disappeared above 250 °C and was speculated to be a titanium acid (H2Ti2O5.H2O). Upon further heating above 250 °C, the anatase phase converted to the high temperature stable TiO2 phase, rutile, also with an increased formation of the expected LTO spinel phase around 850 °C. Keeping the material at 850 °C, isothermally, did show further conversion of the rutile into the desired spinel phase Li4Ti5O12 (LTO) with an increase in the crystallite size and a decrease in surface area. SEM analysis of the material at 850 °C did show some extensive sintering of the particles with some samples indicating the presence of an additional β-Li2TiO3 phase that formed at the high temperatures. Upon cooling, the βLi2TiO3 phase showed a distinctive powder diffraction pattern besides the typical spinel II LTO phase. The study showed that in comparison to the oxide formed at 850 °C, a mixed phase material of the spinel LTO, anatase and rutile could be achieved at temperatures close to 650 °C with very small crystallites and a relatively large surface area that showed desirable electrochemical properties. Suitable Li-ion coin cells were built with the undoped spinel and doped materials that were isothermally made at 650 °C and 850 °C, whereby their electrochemical properties were tested in the form of cell capacity, electrochemical impedance spectroscopy (EIS) and differential capacity (dQ/dV) studies. The cells made with the materials at 850 °C provided reasonable capacity where the dQ/dV plots did show a single step redox reaction at around 1.5V vs Li/Li+ . These were compared to cells made with commercially available LTO and highlighted the importance of high surface area and small particle size of the active material in order to achieve acceptable electrochemical performances. The cells with the materials made at 650 °C showed to have good capacity upon the first discharge with a number of irreversible phase transitions that were subsequently not observed upon recharging. The dQ/dV graphs showed that the phase transitions were unique to the mixed phase composition of the material made at low temperatures and the cells made with the doped spinel materials were on average better performing than the undoped LTO material. Subsequent grinding steps of the active material made at 850 °C improved the capacity performance of the cells but were still lower when compared to the commercially available material. Hence, significantly longer grinding and processing time would be required to achieve battery active materials that are acceptable for commercial use. This study highlights the importance of understanding the phase transitions that occur during the synthesis route of making battery active material, where doping with different elements and using lower temperatures during synthesis could lead to electroactive materials that do not require additional excessive processing steps such as grinding.
- Format
- ii, 148 leaves
- Format
- Publisher
- Nelson Mandela University
- Publisher
- Faculty of Science
- Language
- English
- Rights
- Nelson Mandela University
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NMU School of Computer Science, Mathematics, Physics and Statistics
| Thumbnail | File | Description | Size | Format | |||
|---|---|---|---|---|---|---|---|
| View Details Download | SOURCE1 | Gelant C Final copy of dissertation April 2020.pdf | 8 MB | Adobe Acrobat PDF | View Details Download |