Development of alternative cathodes that have high capacity and long cycle life at an affordable cost is critical for next generation rechargeable batteries to meet the ever-increasing requirements of global energy storage market. Lithium-sulfur batteries, employing sulfur cathodes, are increasingly being investigated due to their high theoretical capacity, low cost, and environmental friendliness. However, the practicality of lithium-sulfur technology is hindered by technical obstacles, such as short shelf and cycle life, arising from the shuttling of polysulfide intermediates between the cathode and the anode as well as the poor electronic conductivity of sulfur and the discharge product Li2S. This dissertation focuses on overcoming some of these problems. The sulfur cathode involves an electrochemical conversion reaction compared to the conventional insertion-reaction cathodes. Therefore, modifications in cell-component configurations/structures are needed to realize the full potential of lithium-sulfur cells. This dissertation explores various custom and functionalized cell components that can be adapted with pure sulfur cathodes, e.g., porous current collectors in Chapter 3, interlayers in Chapter 4, sandwiched electrodes in Chapter 5, and surface-coated separators in Chapter 6. Each chapter introduces the new concept and design, followed by necessary modifications and development. The porous current collectors embedded with pure sulfur cathodes are able to contain the active material in their porous space and ensure close contact between the insulating active material and the conductive matrix. Hence, a stable and reversible electrochemical-conversion reaction is facilitated. In addition, the use of highly porous substrates allows the resulting cell to accommodate high sulfur loading. The interlayers inserted between the pure sulfur cathode and the separator effectively intercept the diffusing polysulfides, suppress polysulfide migration, localize the active material within the cathode region, and boost cell cycle stability. The combination of porous current collectors and interlayers offers sandwiched electrode structure for the lithium/dissolved polysulfide cells. By way of integrating the advantages from the porous current collector and the interlayer, the sandwiched electrodes stabilize the dissolved polysulfide catholyte within the cathode region, resulting in a high discharge capacity, long-term cycle stability, and high sulfur loading. The novel surface-coated separators have a polysulfide trap or filter coated onto one side of a commercial polymeric separator. The functional coatings possess physical and/or chemical polysulfide-trapping capabilities to intercept, absorb, and trap the dissolved polysulfides during cell discharge. The functional coatings also have high electrical conductivity and porous channels to facilitate electron, lithium-ion, and electrolyte mobility for reactivating the trapped active material. As a result, effective reutilization of the trapped active material leads to improved long-term cycle stability. The investigation of the key electrochemical and engineering parameters of these novel cell components has allowed us to make progress on (i) understanding the materials chemistry of the applied functionalized cell components and (ii) the electrochemical performance of the resulting lithium-sulfur batteries. / text