Three LiCoO2 samples of different specifications were synthesized using different Co3O4s as starting material, and characterized in physical, electrochemical and safety properties. There demonstrates clear dependence ...Three LiCoO2 samples of different specifications were synthesized using different Co3O4s as starting material, and characterized in physical, electrochemical and safety properties. There demonstrates clear dependence of LiCoO2 on Co3O4 in particle size and density. The main difference among the three LiCoO2 samples lies in physical, rate capability and safety properties, the sample with larger particle size, higher density （accordingly smaller surface area） demonstrates better safety but lower rate capability, while there is little difference among them in terms of capacity and cycling stability despite of the variation in physical properties.展开更多
Ni-rich layered cathode is regarded as one of the most promising candidates to achieve lithium-ion batteries (LIBs) with high energy density. However, due to the irreversible phase transformation (IPT) and its eventua...Ni-rich layered cathode is regarded as one of the most promising candidates to achieve lithium-ion batteries (LIBs) with high energy density. However, due to the irreversible phase transformation (IPT) and its eventual propagation from surface to the bulk of the material, Ni-rich layered cathode typically suffers from severe capacity fading, structure failure, and thermal instability, which greatly hinders its mass adoption. Hence, achieving an in-depth understanding of the IPT propagation mechanism in Ni-rich layered cathode is crucial in addressing these issues. Herein, the triggering factor of IPT propagation in Ni-rich cathode is verified to be the initial surface disordered cation mixing domain covered by a thin rock-salt phase, instead of the rock-salt phase itself. According to the density functional theory (DFT) results, it is further illustrated that the metastable cation mixing domain possesses a lower Ni migration energy barrier, which facilitates the migration of Ni ions towards the Li slab, and thus driving the propagation of IPT from surface to the bulk of the material. This finding clarifies a prevailing debate regarding the surface impurity phases of Ni-rich cathode material and reveals the origin of IPT propagation, which implies the principle and its effectiveness of tuning the surface microstructure to address the structural and thermal instability issue of Ni-rich layered cathode materials.展开更多
文摘Three LiCoO2 samples of different specifications were synthesized using different Co3O4s as starting material, and characterized in physical, electrochemical and safety properties. There demonstrates clear dependence of LiCoO2 on Co3O4 in particle size and density. The main difference among the three LiCoO2 samples lies in physical, rate capability and safety properties, the sample with larger particle size, higher density （accordingly smaller surface area） demonstrates better safety but lower rate capability, while there is little difference among them in terms of capacity and cycling stability despite of the variation in physical properties.
基金This work was supported by the National Key R&D Program of China(2016YFB0100301)National Natural Science Foundation of China(21875022,51802020)+2 种基金the Natural Science Foundation of Chongqing,China(cstc2020jcyj-msxmX0654,cstc2020jcyj-msxm X0589)the Science and Technology Innovation Foundation of Beijing Institute of Technology Chongqing Innovation Center(2020CX5100006)the Young Elite Scientists Sponsorship Program by CAST(2018QNRC001).L.Chen,N.Li and D.Y.Cao acknowledge the support from Beijing Institute of Technology Research Fund Program for Young Scholars.
文摘Ni-rich layered cathode is regarded as one of the most promising candidates to achieve lithium-ion batteries (LIBs) with high energy density. However, due to the irreversible phase transformation (IPT) and its eventual propagation from surface to the bulk of the material, Ni-rich layered cathode typically suffers from severe capacity fading, structure failure, and thermal instability, which greatly hinders its mass adoption. Hence, achieving an in-depth understanding of the IPT propagation mechanism in Ni-rich layered cathode is crucial in addressing these issues. Herein, the triggering factor of IPT propagation in Ni-rich cathode is verified to be the initial surface disordered cation mixing domain covered by a thin rock-salt phase, instead of the rock-salt phase itself. According to the density functional theory (DFT) results, it is further illustrated that the metastable cation mixing domain possesses a lower Ni migration energy barrier, which facilitates the migration of Ni ions towards the Li slab, and thus driving the propagation of IPT from surface to the bulk of the material. This finding clarifies a prevailing debate regarding the surface impurity phases of Ni-rich cathode material and reveals the origin of IPT propagation, which implies the principle and its effectiveness of tuning the surface microstructure to address the structural and thermal instability issue of Ni-rich layered cathode materials.
