The structure instability and cycling decay of silicon (Si) anode triggered by stress buildup hinder its practical application to next-generation high-energy–density lithium-ion batteries (LIBs). Herein, a cross-linking polymeric network as a self-healing binder for Si anode is developed by in situ polymerization of tannic acid (TA) and polyacrylic acid (PAA) binder labelled as TA-c-PAA. The branched TA as a physical cross-linker complexes with PAA main chains through abundant dynamic hydrogen bonds, endowing the cross-linking TA-c-PAA binder with unique self-healing property and strong adhesion for Si anode. Benefiting from the mechanical robust and hard adhesion, the Si@TA-c-PAA electrode exhibits high reversible specific capacities (3250 mAh/g at 0.05C (1C = 4000 mA g⁻¹)), excellent rate capability (1599 mAh/g at 2C), and impressive cycling stability (1742 mAh/g at 0.25C after 450 cycles). After Ex situ morphology characterization, in situ swelling analysis, and finite element simulation, it is found that the TA-c-PAA binder allows the Si anode to dissipate stress and prevent pulverization during lithiation and delithiation, thus the hydrogen bonds among interpenetrating network may be adaptable to the stress intensity. Our work paves a new avenue for the design of efficient and cost-effective binders for next-generation Si anode in LIBs.

硅（Si）阳极的结构不稳定性和由应力累积引发的循环衰减阻碍了其在下一代高能量密度锂离子电池（LIB）中的实际应用。在此，通过单宁酸（TA）和聚丙烯酸（PAA）粘合剂的原位聚合开发了一种作为硅阳极自修复粘合剂的交联聚合物网络，标记为TA-c-PAA。支化TA作为物理交联剂通过丰富的动态氢键与PAA主链络合，赋予交联TA-c-PAA粘合剂独特的自修复性能和对硅阳极的强附着力。得益于机械强度和硬粘附力，Si@TA-c-PAA电极表现出高可逆比容量（3250 mAh/g @ 0.05C (1C = 4000 mA g ⁻¹ )）、优异的倍率性能（1599 mAh/g） 2C 时），以及令人印象深刻的循环稳定性（450 次循环后，0.25C 时为 1742 mAh/g）。经过非原位形貌表征、原位溶胀分析和有限元模拟，发现TA-c-PAA粘合剂可以使硅阳极在锂化和脱锂过程中消散应力并防止粉化，从而使互穿网络之间的氢键可以发挥作用。适应压力强度。我们的工作为设计下一代锂离子电池硅阳极的高效且经济高效的粘合剂铺平了一条新途径。