Re‐Engineering Poly(Acrylic Acid) Binder toward Optimized Electrochemical Performance for Silicon Lithium‐Ion Batteries: Branching Architecture Leads to Balanced Properties of Polymeric Binders

Silicon is a promising anode material for lithium‐ion batteries with its superior capacity. However, the drastic volume changes during lithiation/delithiation cycles hinder the cycling performance, resulting in particle pulverization, conductivity loss, and an unstable electrode–electrolyte interface. Herein, a series of synthetic polymeric binders, poly(acrylic acid‐co‐tetra(ethylene glycol) diacrylate)—featuring a poly(acrylic acid) (PAA) backbone branched via tetra(ethylene glycol) diacrylate (TEGDA)—are developed that edge toward evidencing well‐balanced properties to confront capacity fading in Si‐based electrodes. The incorporation of ether chain not only leads to the branching architecture of the PAA backbone, thus affecting its mechanical properties, but also promotes the conductivity of Li ions. As a result, a synergistic performance improvement is observed in both half and full cells. The best‐performing cell using a branched PAA binder (bPAA) with a feeding molar ratio ([TEGDA]:[acrylic acid(AA)]) of 0.2 results in a 10% increase in initial capacity and a 31% increase in capacity retention over 100 cycles compared to the linear PAA cell. The cross‐sectional microscopic images of the cycled electrodes reveal that bPAA binders can drastically reduce the electrode expansion. This improvement results from the well‐balanced properties of the polymer design, which could guide further development for more advanced binder materials. The silicon anode is a promising candidate to enable high energy density lithium‐ion batteries. To alleviate huge volume changes in silicon during cycling, a branched poly(acrylic acid) (PAA) binder is developed featuring an ether containing cross‐linker. The branched polymer binder shows improved mechanical properties, lower glass transition temperature, higher conductivity, and improved cycling performance compared to linear PAA.