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Thermal stability is one of the critical requirements for commercial operation of high energy lithium-ion batteries. In this study, we use in situ X-ray diffraction technique to elucidate the thermal degradation mechanism of 0.5Li 2 MnO 3 -0.5LiNi 0.33 Co 0.33 Mn 0.33 O 2 lithium rich cathode material in the absence and presence of electrolyte to simulate the real life battery conditions and compare its thermal behavior with the commercial LiNi 0.33 Co 0.33 Mn 0.33 O 2 cathode material. We show that the thermal induced phase transformations in delithiated lithium rich cathode material are much more intense compared to similar single phase layered cathode material in the presence of electrolyte. The structural changes in both cathode materials with the temperature rise follow different trends in the absence and presence of electrolyte between 25 and 600 °C. Phase transitions are comparatively simple in the absence of electrolyte, the fully charged lithium rich cathode material demonstrates better thermal stability by maintaining its phase till 379 °C, and afterwards spinel structure is formed. In the presence of electrolyte, however, the spinel structure appears at 207 °C, subsequently it transforms to rock salt type cubic phase at 425 °C with additional metallic, metal fluoride, and metal carbonate phases.

A new synthetic method using biotemplating for fabrication of LiCoO2 (LCO) for batteries of mobile products is developed. The LCO can be manufactured in various forms, and rapidly charged and discharged, even when using a thick electrode. Among three types of candidate biotemplates wood, cotton, and grass pollen, cotton was selected as the biotemplate considering its performance and potential for commercialization. Both the size of the primary particle and the shape of the secondary particle are controllable by using cotton. When using a thin electrode, the difference in capacitance between the LCO fabricated by the general method (solid-LCO) and the LCO made by using cotton (cotton-LCO) is within 3%, regardless of current density. On the other hand, the capacity difference in the case of a thick electrode between two samples is approximately 1.5 times higher than that observed for solid-LCO at very high current density (6C). The capacity retention values are 1.4% and 75.1% at 6C after the 100th cycle for solid-LCO and cotton-LCO, respectively. The superior performance at high current density for the cotton-LCO likely arises from decreasing the distance that the Li+ ion must diffuse in the solid-state by connected nanoparticles.

Direct internal pressure measurements of the cylindrical Li-ion cells with a mixture of LiCoO 2 and Li 1.167 Ni 0.233 Co 0.1 Mn 0.467 Mo 0.033 O 2 (a solid solution between 0.4 Li 2 Mn 0.8 Ni 0.1 Mo 0.1 O 3 and 0.6 LiNi 0.4 Co 0.2 Mn 0.4 O 2 ) as cathode and graphite as anode have been performed during cell charging. Cell internal pressure at the end of charging is greatly reduced from 2.85 to 0.84–1.84 bar by adding a small amount of phosphorus derivatives such as triphenyl phosphine (TPP), ethyl diphenylphosphinite (EDP), and triethyl phosphite (TEP) into a carbonate-based electrolyte. The phosphorus derivatives are supposed to react with O 2 generated from the decomposition of the Li 2 MnO 3 component. The chemical states of additive molecules before and after the charging process have been characterized with a nuclear magnetic resonance (NMR) spectroscopy and gas chromatography–mass spectrometry (GC–MS). It has also been shown that those additives improve the cycle life when applied in coin full cells.