storage and engineering heterogeneous structure for lithium transfer are the key for improving the energy density and rate performance of LIBs. [4][5][6][7][8] Silicon (Si), a naturally abundant material with outstanding theoretical capacity (4200 mAh g −1 ), has attracted extensive attention as an alternative promising anode for high-energydensity LIBs, which is ten times larger than the conventional graphite anode (372 mAh g −1 ). [9][10][11][12] However, Si inherently has large volume change that seriously undermines electrode integrity and solid electrolyte interface (SEI) film formed on the Si surface. Repairing and growth of the SEI film leads to reduced amount of available Liions, corresponding to the capacity decline of LIBs. [13][14][15] Generally, engineering Si materials is widely adopted to relieve the influence of large volume change and enhance lithium diffusion within the electrode. [16][17][18] However, high cost is barely accepted into the industry due to complex preparation process. Furthermore, most methods are not based on the mass-loading-oriented strategy for high-energy-density LIBs. [19] Binder is the key component in the electrode to bond active material and conductive additive together on current collector and keep electrode integrity during charge/discharge processes. [20][21][22] Recently, the functions of the binders, such as N-P-LiPN) is constructed by the partially lithiated hard polyacrylic acid as a framework and partially lithiated soft Nafion as a buffer via the hydrogen binding effect. N-P-LiPN has strong adhesion and mechanical properties to accommodate huge volume change of the Si anode. In addition, lithiumions are transferred via the lithiated groups of N-P-LiPN, which significantly enhances the ionic conductivity of the Si anode. Hence, the Si@N-P-LiPN electrodes achieve the highest initial Coulombic efficiency of 93.18% and a stable cycling performance for 500 cycles at 0.2 C. Specially, Si@N-P-LiPN electrodes demonstrate an ultrahigh-areal-capacity of 49.59 mAh cm −2 . This work offers a new approach for inspiring the battery community to explore novel binders for next-generation high-energy-density storage devices.
High-capacity electrode materials play a vital role for high-energy-density lithium-ion batteries. Silicon (Si) has been regarded as a promising anode material because of its outstanding theoretical capacity, but it suffers from an inherent volume expansion problem. Binders have demonstrated improvements in the electrochemical performance of Si anodes. Achieving ultrahigh-areal-capacity Si anodes with rational binder strategies remains a significant challenge. Herein, a binder-lithiated strategy is proposed for ultrahigh-areal-capacity Si anodes. A hard/soft modulated trifunctional network binder (