Microporous battery separators

H. Lee, M. Alcoutlabi, J.V. Watson, X. Zhang, Polyvinylidene fluoride-co-chlorotriflu-oroethylene and polyvinylidene fluoride-co-hexafluoropropylene nanoflber-coated polypropylene microporous battery separator membranes. Journal of Polymer Science, Part B Polymer Physics 51 (5) (2013) 349-357. 

Yu WC (2005) Continuous methods of making microporous battery separators. US Patent 6,878,226... 

Lee H, Alcoutlabi M, Watson JV, Zhang X (2013) Polyvinylidene fluoride-co-chlorotrifluoroethylene and polyvinylidene fluoride-co-hexafluoropropylene nanofiber-coated polypropylene microporous battery separator membranes. J Polym Sd Part B-Polym Phys 51(5) 349-357. doi 10.1002/polb.23216... 

In the second half of the 1960s, at the same time but independently, three basically different plastic separators were developed. One was the polyethylene separator [16] already referred to in starter batteries, used only rarely in stationary batteries, but successful in traction batteries. The others were the microporous phenolic resin separator (DARAK) [18] and a microporous PVC separator [19], both of which became accepted as the standard separation for stationary batteries. They distinguish themselves by high porosity (about 70 percent) and thus very low electrical resistance and very low acid displacement, both important criteria for stationary batteries. 

Electric road vehicles have been reduced to insignificance, as mentioned already by, vehicles with combustion engines. Another electric vehicle — the electrically driven submarine — presented a continuous challenge to lead-acid battery separator development since the 1930s and 1940s. The wood veneers originally used in electric vehicles proved too difficult to handle, especially if tall cells had to be manufactured. Therefore much intense effort took place to develop the first plastic separators. In this respect the microporous hard rubber separator, still available today in a more advanced version, and a micro-porous PVC separator (Porvic I) merit special mention 28]. For the latter a molten blend of PVC, plasticizer and starch was rolled into a flat product. In a lengthy pro-... 

Much of the above also holds true for the application of microporous PVC separators (see Sec. 9.2.3.1) in open stationary batteries. Very high porosity and thus low acid displacement and electrical resistance are also offered by this system. The relevant properties are compiled in Table 12. 

Battery makers sometimes view separators with disdain the separator is needed but does not actively contribute to battery operation. Consequently, very little work (relative to that on electrode materials and electrolytes) is directed towards characterizing separators. In fact, development efforts are under way to displace microporous membranes as battery separators and instead to use gel electrolytes or polymer electrolytes. Polymer electrolytes, in particular, promise enhanced safety by elimi-... 

Fignre 27.3 shows a typical spectroelectrochemical cell for in sitn XRD on battery electrode materials. The interior of the cell has a construction similar to a coin cell. It consists of a thin Al203-coated LiCo02 cathode on an aluminum foil current collector, a lithium foil anode, a microporous polypropylene separator, and a nonaqueous electrolyte (IMLiPFg in a 1 1 ethylene carbonate/dimethylcarbonate solvent). The cell had Mylar windows, an aluminum housing, and was hermetically sealed in a glove box. 

Lithium secondary batteries can be classified into three types, a liquid type battery using liquid electrolytes, a gel type battery using gel electrolytes mixed with polymer and liquid, and a solid type battery using polymer electrolytes. The types of separators used in different types of secondary lithium batteries are shown in Table 1. The liquid lithium-ion cell uses microporous polyolefin separators while the gel polymer lithium-ion cells either use a PVdF separator (e.g. PLION cells) or PVdF coated microporous polyolefin separators. The PLION cells use PVdF loaded with silica and plasticizer as separator. The microporous structure is formed by removing the plasticizer and then filling with liquid electrolyte. They are also characterized as plasticized electrolyte. In solid polymer lithium-ion cells, the solid electrolyte acts as both electrolyte and separator. 

In lithium-based cells, the essential function of battery separator is to prevent electronic contact, while enabling ionic transport between the positive and negative electrodes. It should be usable on highspeed winding machines and possess good shutdown properties. The most commonly used separators for primary lithium batteries are microporous polypropylene membranes. Microporous polyethylene and laminates of polypropylene and polyethylene are widely used in lithium-ion batteries. These materials are chemically and electrochemically stable in secondary lithium batteries. 

Abraham et al. were the first ones to propose saturating commercially available microporous polyolefin separators (e.g., Celgard) with a solution of lithium salt in a photopolymerizable monomer and a nonvolatile electrolyte solvent. The resulting batteries exhibited a low discharge rate capability due to the significant occlusion of the pores with the polymer binder and the low ionic conductivity of this plasticized electrolyte system. Dasgupta and Ja-cobs patented several variants of the process for the fabrication of bonded-electrode lithium-ion batteries, in which a microporous separator and electrode were coated with a liquid electrolyte solution, such as ethylene—propylenediene (EPDM) copolymer, and then bonded under elevated temperature and pressure conditions. This method required that the whole cell assembling process be carried out under scrupulously anhydrous conditions, which made it very difficult and expensive. 

Lithium CFj. The Li/CF rbattery consists of a lithium anode, polycarbon monofluoride cathode, and microporous polypropylene separator saturated with organic electrolyte. These batteries are used as power sources for watches, portable calculators, memory applications, and so on. 

The battery separator currently used by most flooded cell type lead-acid battery manufacturers are of the microporous PE type. It was invented in the late 1960s by W. R. Grace Co. The term... 

Wang. L. C. Harvey, M. K. Stein, H. L. Scheunemann, U. The Role of UHMW-PE in Microporous PE Separators. Proceedings of the 12th Annual Battery Conference on Applications Advances, IEEE New York, 1997 p 69. 

Producing polyethylene microporous film with a porosity of 20 to 80% for battery separators. ... 

Conventional shutdown temperatures are around 130°C. However, a microporous polyolefin battery separator with a shutdown temperature of 95-110°C and a melt integrity of more than 165°C can be made from a basic UHMWPE formulation (38). 

Saunier, AUoin, E, Sanchez, J.-Y., Maniguet, L, 2004. Plasticized microporous PVdF separators for lithium ions batteries. Part 111 gel properties and irreversible modifications of PolyfvinyUdene fluoride) membranes under swelling in liquid electrolyte. J. Polym. Sci. Part B 42,2308-2317. 

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