In Situ Synthesis of Hierarchical Core Double‐Shell Ti‐Doped LiMnPO 4 @NaTi 2 (PO 4 ) 3 @C/3D Graphene Cathode with High‐Rate Capability and Long Cycle Life for Lithium‐Ion Batteries

• Published in: Advanced energy materials 2019-03, Vol.9 (11)
• Main Authors: Liang, Longwei, Sun, Xuan, Zhang, Jinyang, Hou, Linrui, Sun, Jinfeng, Liu, Yang, Wang, Shuguang, Yuan, Changzhou
• Format: Article
• Language: English
• ISSN: 1614-6832; 1614-6840
• DOI: 10.1002/aenm.201802847

Olivine‐type LiMnPO 4 (LMP) cathodes have gained enormous attraction for Li‐ion batteries (LIBs), thanks to their large theoretical capacity, high discharge platform, and thermal stability. However, it is still hugely challenging to achieve encouraging Li‐storage behaviors owing to their low electronic conductivity and limited lithium diffusion. Herein, the core double‐shell Ti‐doped LMP@NaTi 2 (PO 4 ) 3 @C/3D graphene (TLMP@NTP@C/3D‐G) architecture is designed and constructed via an in situ synthetic methodology. A continuous electronic conducting network is formed with the unfolded 3D‐G and conducting carbon nanoshell. The Nasicon‐type NTP nanoshell with exceptional ionic conductivity efficiently inhibits gradual enrichment in by‐products, and renders low surfacial/interfacial electron/ion‐diffusion resistance. Besides, a rapid Li + diffusion in the bulk structure is guaranteed with the reduction of Mn Li+ ˙ antisite defects originating from the synchronous Ti‐doping. Benefiting from synergetic contributions from these design rationales, the integrated TLMP@NTP@C/3D‐G cathode yields high initial discharge capacity of ≈164.8 mAh g −1 at 0.05 C, high‐rate reversible capacity of ≈116.2 mAh g −1 at 10 C, and long‐term capacity retention of ≈93.3% after 600 cycles at 2 C. More significantly, the electrode design developed here will exert significant impact upon constructing other advanced cathodes for high‐energy/power LIBs.