Energy storage technologies with increased energy densities and lifetimes are needed for the advancement of electric and hybrid electric vehicles and storage of intermittent renewable energy, among other technologies with significant energy needs. High capacity anode materials that can alloy with lithium, such as silicon, hold great promise towards advancing the energy density of lithium-ion batteries, a major component of the energy storage sector. However, silicon anodes undergo catastrophic volumetric expansion as lithium ions react with silicon in the anode resulting in silicon particle fracture, delamination, and disruption of the electrical network in the electrode during cycling, eventually resulting in failure. One method to address failure of silicon anodes is through the development of novel polymeric binders, which can mitigate or prevent damage during cycling by suppressing cracking, adhering strongly to silicon and copper, and passivating the silicon anode surface. In this thesis, we explore the design, development, and characterization of novel polymeric binder materials for silicon anodes, in particular connecting physical properties of polymeric binders to specific design principles. In the first chapter, we review the development of novel polymeric binders with an emphasis on guiding design principles and characterization techniques. In the second chapter, we study a molecular weight series of high-modulus and high adhesion partially hydrolyzed polyacrylamide (HPAM) binders. Model and composite electrodes prepared with varying molecular weight of the polymer binder are analyzed to correlate physical properties to electrochemical behavior trends and failure modes of the binders. We attribute capacity decay in these materials due to poor lithium ion mobility, eventually leading to fraction and isolation of silicon. In another chapter, a series of conductive PEDOT:PSS conjugated polymer binders are crosslinked using three different chemistries and characterized with respect to mechanical properties, adhesion, electrochemical stability, cycling capacity and stability. Crosslinking is found to enhance performance, and poor cycling stability is attributed to poor adhesion to silicon and copper. This work systematically investigates and quantifies the physical properties of polymeric binders relevant to electrode stability and performance.