Low-Cost Production of Lithium-Ion Separator Membranes w/ Improved Safety
The purpose of this Cooperative Research and Development Agreement (CRADA) between Oak Ridge National Laboratory (ORNL) and Porous Power Technologies, LLC (PPT) was to validate the performance, durability, and safety of a new type of reinforced, composite lithium ion battery separator produced as either a free-standing product or by a method of direct coating after electrode fabrication. ORNL’s primary roles were to develop novel separator thermophysical and mechanical property characterization methods and assist with fundamental understanding of SYMMETRIX® HPX and HPX-F product line chemical makeup and microstructure. PPT’s primary roles were to implement the understanding gained from the ORNL developed characterization methods into a refined product line featuring nonwoven-reinforced, ceramic-filled composite HPX-F separators for the lithium ion battery industry and quantify long-term cell performance improvements associated with HPX-F separators. Over the course of this CRADA, the product line of PPT was expanded from a pure polyvinylidene fluoride (PVDF) HP and polyester nonwoven-reinforced HPX separator platform to one that includes a variety of ceramic-filled HPX-F separators. In addition, the laminating and direct coating technologies for HPX and HPX-F separators are now more developed and moving towards commercial licensing. PPT’s SYMMETRIX® production process will revolutionize the production of lithium ion batteries by eliminating one of the most expensive components (the free-standing separator membrane) while improving performance and safety. The performance and safety improvements are due primarily to replacement of the conventional polyethylene/polypropylene (PE/PP) separator material with polyvinylidene fluoride (PVDF), and to ceramic materials added to the PVDF to form a short-resistant, thermally-stable composite structure. Ultimately, lithium ion battery manufacturers will be able to produce PPT separators in-house through the laminating or direct coating methods such as those based on the SYMMETRIX® product line, giving them higher performance cells at a fraction of the cost required to purchase separators from existing vendors. Direct coating of separators onto electrodes eliminates the cost of a downstream thermal lamination step and requires little or no change to existing equipment. It is a clear path for lithium ion battery manufacturers to reach the <$1/m2 separator price target set by the U.S. Advanced Battery Consortium (USABC). The technology enabled by this project will have a substantial impact on energy efficiency required to produce cells and is anticipated to save up to $1B annually by 2014 in reduced manufacturing costs. In addition, it will contribute significantly to production energy savings associated with transporting free-standing polyolefin (PE/PP) separators from the vendor to the cell manufacturer locations. SYMMETRIX® separators have shown increased cell capacity, improved thermal stability, and longer cycle life over their PE/PP counterparts and have been repeatedly demonstrated to improve nearly all aspects of lithium ion battery performance Prior to the start of this CRADA, widespread adoption has been limited by three factors: 1) difficulty in handling the material on high-speed processing equipment due to lower tensile strength than oriented PE/PP materials; 2) cost concerns associated with the higher expense of PVDF as a raw material; and 3) questions regarding short resistance and durability. The first factor was addressed through thorough mechanical (ultimate tensile strength and dynamic mechanical analysis, etc.) property characterization of HPX and HPX-F materials against the commercial polyolefin baselines. The second factor was address by shifting the focus of PPT’s product line towards the HPX-F materials with low-PVDF (high ceramic filler) content to reduce overall separator cost. Concerns associated with the third factor were alleviated by evaluating the internal shorting resistance of the separators using a custom developed ORNL measurement method and obtaining long-term cycling data of the new HPX-F separator formulations. A materials emphasis was placed on polyester fiber mats for the nonwoven reinforcement (to boost overall separator tensile strength) and proprietary metal oxides for the HPX-F fillers (to improve thermomechanical properties of the separator and make it more resistant to overcharge and internal shorting).