Separators lithium batteries

The liquid electrolytes used in lithium batteries can be gelled by addition of a polymer [25] or fumed silica [26], or by cross linking of a dissolved monomer [271. Depending on the mechanical properties, gelled electrolytes can be used as separators, or supported by a conventional [27]... 

Aprotic electrolytes of an adequate high conductivity are necessary for lithium batteries and super capacitors. Therefore, recently, much industrial research has been done in this area and highly sophisticated electrolyte systems have been developed (e.g. [64]). The supporting electrolytes for aprotic solvents generally are more or less expensive and toxic. After the reaction, their separation and recycling is inevitable and frequently needs considerable efforts. 

At this time the only commercially available all-solid-state cell is the lithium battery containing Lil as the electrolyte. Many types of solid lithium ion conductors including inorganic crystalline and glassy materials as well as polymer electrolytes have been proposed as separators in lithium batteries. These are described in the previous chapters. A suitable solid electrolyte for lithium batteries should have the properties... 

Both batteries and fuei cells utilize controlled chemical reactions in which the desired process occurs electrochemically and all other reactions including corrosion are hopefully absent or severely kinetically suppressed. This desired selectivity demands careful selection of the chemical components including their morphology and structure. Nanosize is not necessarily good, and in present commercial lithium batteries, particle sizes are intentionally large. All batteries and fuel cells contain an electropositive electrode (the anode or fuel) and an electronegative electrode (the cathode or oxidant) between which resides the electrolyte. To ensure that the anode and cathode do not contact each other and short out the cell, a separator is placed between the two electrodes. Most of these critical components are discussed in this thematic issue. 

A battery is a transducer that converts chemical energy into electrical energy and vice versa. It contains an anode, a cathode, and an electrolyte. The anode, in the case of a lithium battery, is the source of lithium ions. The cathode is the sink for the lithium ions and is chosen to optimize a number of parameters, discussed below. The electrolyte provides for the separation of ionic transport and electronic transport, and in a perfect battery the lithium ion transport number will be unity in the electrolyte. The cell potential is determined by the difference between the chemical potential of the lithium in the anode and cathode, AG = —EF. 

An ideal electrolyte solute for ambient rechargeable lithium batteries should meet the following minimal requirements (1) It should be able to completely dissolve and dissociate in the nonaqueous media, and the solvated ions (especially lithium cation) should be able to move in the media with high mobility. (2) The anion should be stable against oxidative decomposition at the cathode. (3) The anion should be inert to electrolyte solvents. (4) Both the anion and the cation should remain inert toward the other cell components such as separator, electrode substrate. 

There is not too much information available on the battery separator market in the literature. It is estimated that about 30% of the rechargeable lithium battery market or 1.5 billion is the size of the battery materials or components market. Battery separators for lithium batteries are about a 330 million market within the total battery components market. ° Recently, the Freedonia Group has reported that the U.S. demand for battery separators will increase to 410 million in 2007 from 237 million in 1977 and 300 million in 2002, respectively. ... 

In most batteries, the separators are either made of nonwoven fabrics or microporous polymeric films. Batteries that operate near ambient temperatures usually use separators fabricated from organic materials such as cellulosic papers, polymers, and other fabrics, as well as inorganic materials such as asbestos, glass wool, and Si02. In alkaline batteries, the separators used are either regenerated cellulose or microporous polymer films. The lithium batteries with organic electrolytes mostly use microporous films. 

They are fabricated from a variety of inorganic, organic, and naturally occurring materials and generally contain pores that are greater than 50—100 A in diameter. Materials such as nonwoven fibers (e.g. nylon, cotton, polyesters, glass), polymer films (e.g. polyethylene (PE), polypropylene (PP), poly(tetrafluo-roethylene) (PTFE), poly (vinyl chloride) (PVC)), and naturally occurring substances (e.g. rubber, asbestos, wood) have been used for microporous separators in batteries that operate at ambient and low temperatures (<100 °C). The microporous polyolefins (PP, PE, or laminates of PP and PE) are widely used in lithium based nonaqueous batteries (section 6.1), and filled polyethylene separators in lead-acid batteries (section 7.3), respectively. 

Table 1. Types of Separators Used in Different Type of Secondary Lithium Batteries...

All lithium based batteries use nonaqueous electrolytes because of the reactivity of lithium in aqueous solution and because of the electrolyte s stability at high voltage. The majority of these cells use microporous membranes made of polyolefins. In some cases, nonwovens made of polyolefins are either used alone or with microporous separators. This section will mainly focus on separators used in secondary lithium batteries followed by a brief summary of separators used in lithium primary batteries. 

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. 

Nonwoven materials such as cellulosic fibers have never been successfully used in lithium batteries. This lack of interest is related to the hygroscopic nature of cellulosic papers and films, their tendency to degrade in contact with lithium metal, and their susceptibility to pinhole formation at thickness of less than 100 fjim. For future applications, such as electric vehicles and load leveling systems at electric power plants, cellulosic separators may find a place because of their stability at higher temperatures when compared to polyolefins. They may be laminated with polyolefin separators to provide high-temperature melt integrity. 

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. 

Pore Size. A key requirement of separators for lithium batteries is that their pores be small enough to prevent dendritic lithium penetration through them. Membranes with submicrometer pore sizes have proven adequate for lithium batteries. 

Figure 4. Scanning electron micrographs of the surface of single layer Celgard separators used in lithium batteries (a) 2400 (PP), (b) 2500 (PP), and (c) 2730 (PE).

To overcome the poor mechanical properties of polymer and gel polymer type electrolytes, microporous membranes impregnated with gel polymer electrolytes, such as PVdF. PVdF—HFP. and other gelling agents, have been developed as an electrolyte material for lithium batteries.Gel coated and/ or gel-filled separators have some characteristics that may be harder to achieve in the separator-free gel electrolytes. For example, they can offer much better protection against internal shorts when compared to gel electrolytes and can therefore help in reducing the overall thickness of the electrolyte layer. In addition the ability of some separators to shutdown... 

Table 8. Separators and Their Manufacturers for Major Primary Lithium Battery Systems...

Hying, C. Separion separators for lithium batteries—safety performance. Presented at Batteries 2004, 6th Ed. Paris, June 2-4, 2004. 

Recall that a battery is an electrochemical device having an anode, a cathode, an electrolyte, and a separator sandwiched between the anode and the cathode and impregnated with the electrolyte. Membranes with filler are used preferably in lead acid batteries. Membranes without filler are used preferably in lithium batteries. 

Y. Sudou, H. Suzuki, S. Nagami, K. Ikuta, T. Yamamoto, S. Okijima, S. Suzuki, and H. Ueshima, Separator for battery and lithium ion battery using the same, US Patent 7183 020, assigned to Mitsui Chemicals, Inc. (Tokyo, JP) Denso Corporation (Aichi, JP), February 27, 2007. 

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