Understanding the electrochemical properties and safety characteristics of spinel cathodes for lithium-ion batteries
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Manganese spinel cathodes LiMn₂O₄ offer the advantage of a strong, edge-shared octahedral framework with fast, 3-dimensional Li⁺-ion conduction. To better understand the safety of these materials, the thermal stability characteristics of spinel oxide and oxyfluoride cathodes Li[subscript 1.1]Mn[subscript 1.9-y]M[subscript y]O₄[subscript-z]F[subscript z] (M = Ni and Al, 0 ≤ y ≤ 0.3, and 0 ≤ z ≤ 0.2) have been investigated systematically. The thermal characteristics are assessed in terms of the onset temperature and reaction enthalpy for the exothermic reaction. The thermal stability increases with decreasing lithium content in the cathode in the charged state. High-voltage spinel cathodes LiMn[subscript 1.5]Ni[subscript 0.5]O₄ are promising candidates for electric vehicles and stationary storage of electricity produced by renewable energies due to their high power capability. However, widespread adoption of this high-voltage spinel cathode is hampered by severe capacity fade resulting from aggressive reaction with the electrolyte to form a thick solid-electrolyte interphase (SEI) layer. The synthesis conditions of the co-precipitation method are found to influence the microstructure and morphology through nucleation and growth of crystals in solution. Two samples prepared by similar wet-chemical routes have been characterized by microscopy and electrochemical methods to determine the role of microstructure and morphology on the electrochemical performance. It is found that the surface crystal planes play a key role in the capacity retention and rate performance. In order to achieve consistent electrochemical properties essential for the commercialization of the high-voltage spinel cathode LiMn[subscript1.5]Ni[subscript 0.5]O₄, the relationship between cation ordering, presence of impurity phase, and particle morphology must be elucidated. Accordingly, comparison of the stoichiometric LiMn[subscript1.5]Ni[subscript 0.5]O₄ cathodes with a Mn/Ni ratio of 3.0 prepared by different methods having varying morphologies and degrees of cation ordering is presented. It is found that although an increase in the degree of cation ordering decreases the rate capability, the crystallographic planes in contact with the electrolyte have a dominant effect on the electrochemical properties. To examine the effect of cation substitution on morphology, an investigation of the nucleation and growth of doped co-precipitated mixed-metal hydroxide precursor particles and the resulting stabilization of preferred crystallographic surface planes in the final spinel samples are presented. It is found that doping with certain cations stabilizes the growth of low-energy (111) surface planes, facilitating a long cycle life and fast high-rate performance. With an aim to develop a better understanding of the factors influencing the electrochemical properties, a systematic investigation of LiMn[subscript 1.5]Ni[subscript0.5-x]M[subscript x]O₄ (M = Cu and Zn and x = 0.08 and 0.16), in which Ni²⁺ ions are substituted by divalent Cu2+ and Zn2+ ions, is presented. It is found that although both Zn and Cu are divalent with ionic radii similar to that of Ni2+, they behave quite differently with respect to cation ordering and site occupancy, and higher levels of doping leads to distinct differences in cycling and rate performances.