Construction of Hierarchical Conductive Networks for LiNi0.8Mn0.1Co0.1O2 Cathode toward Stable Cycling at High Areal Mass Loadings

Abstract Realizing high‐performance thick electrodes is considered as a practical strategy to promote the energy density of lithium‐ion batteries. However, establishing effective transport pathways for both lithium‐ions and electrons in a thick electrode is very challenging. This study develops a hierarchical conductive network structure for constructing high‐performance NMC811 (LiNi 0.8 Mn 0.1 Co 0.1 O 2 ) cathode toward stable cycling at high areal mass loadings. The hierarchical conductive networks are composed of a Li + /e − mixed conducting interface (lithium polyacrylate/hydroxyl‐functionalized multiwalled carbon nanotubes) on NMC811 particles, and a segregated network of single‐walled carbon nanotubes in the electrode, without any additional binders or carbon black. Such strategy endows the NMC811 cathode (up to 250 µm and 50 mg cm −2 ) with low porosity/tortuosity, ultrahigh Li + /e ‐ conductivities and excellent mechanical property at low carbon nanotube content (1.8 wt%). It significantly improves the electrochemical reaction homogeneity along the electrode depth, meanwhile effectively inhibits the side reactions at the electrode/electrolyte interface and cracks in the NMC particles during cycling. This work emphasizes the crucial role of the electronic/ionic cooperative transportation in the performance deterioration of thick cathodes, and provide guidance for architecture optimization and performance improvement of thick electrodes toward practical applications, not just for the NMC811 cathode.