Thermodynamics-directed bulk/grain-boundary engineering for superior electrochemical durability of Ni-rich cathode

Introducing high-valence Ta element is an essential strategy for addressing the structu ral deterioration of the Ni-rich LiNi_(1-x-y)Co_(x)Mn_(y)O_(2)(NCM)cathode,but the enlarged Li/Ni cation mixing leads to the inferior rate capability originating from the hindered Li~+migration.Note that the non-magnetic Ti~(4+)ion can suppress Li/Ni disorder by removing the magnetic frustration in the transition metal layer.However,it is still challenging to directionally design expected Ta/Ti dual-modification,resulting from the complexity of the elemental distribution and the uncertainty of in-situ formed coating compounds by introducing foreign elements.Herein,a LiTaO_3 grain boundary(GB)coating and bulk Ti-doping have been successfully achieved in LiNi_(0.834)Co_(0.11)Mn_(0.056)O_(2) cathode by thermodynamic guidance,in which the structural formation energy and interfacial binding energy are employed to predict the elemental diffusion discrepancy and thermodynamically stable coating compounds.Thanks to the coupling effect of strengthened structural/interfacial stability and improved Li~+diffusion kinetics by simultaneous bulk/GB engineering,the Ta/Ti-NCM cathode exhibits outstanding capacity retention,reaching 91.1%after 400 cycles at 1 C.This elaborate work contributes valuable insights into rational dual-modification engineering from a thermodynamic perspective for maximizing the electrochemical performances of NCM cathodes.

A new sediment type of coated grain: Oolitic sinter

As a special sedimentary grain type, the coated grain(with an ooid model) has been known for two centuries due to its fascinating special fabric and genesis developments. The leading factors in forming the coated grain consist mainly of:(1) microorganism movement field;(2) chemical sedimentary effect;(3) hydrodynamic force environment and topography condition;(4) abundant core material supply;(5) embedding condition; and(6) humic acids condition in water medium. With the development of the coated grain genesis, the single factor theory cannot reasonably explain the exact formation of the surface sediment of coated grain. Here, we find a new way to study the coated grain on the basis of traditional research methods. The Wenquan area on the northeast edge of the Qiangtang Basin is one of the few areas where the coated grain is developing, and is a rare "natural laboratory" for the study of the coated grain and the thermal spring sediment. The oolitic sinter of the area has the triaxiality modality of pea polymer, and is obviously different from the karst travertine and the normal lacustrine ooid. We found that the hot spring water in the Wenquan area has higher partial pressure of CO2(PCO2) and saturation index of the calcite(SIc) than normal. Macrocosmically, the oolitic sinter is shaped like a pea, and its grains and gap fillings are light yellow. Microcosmically, the sinter grain forms six types of fundamental lamina, and those six types are developed to be four grain types with different combinations. The C-axis of the mineral grain of sinter cement(calcite) is normal to the lamina face, and grows on it with distinct generation formations. In short, the grain type of oolitic sinter is the oncoid, with the grain development caused by the factors such as the shallow water of strong hydrodynamic force, the special hydrochemistry condition, and the extensive algae activities(diatom).