Improved microporous membrane, separator, lithium battery, and related method

Abstract

To provide a battery separator that maintains separation between a cathode and an anode in a battery system, improves high temperature, high energy, high charging rate, and / or high voltage function, improves safety, and / or brings both thermal stability and high temperature physical integrity.SOLUTION: A microporous polyolefin battery separator membrane having a thickness of less than 14 μm, the microporous separator membrane initiates a thermal shutdown at a temperature of 138°C or less, the microporous separator membrane has a machine-direction heat shrinkage of 7.5% or less at 120°C for 1 hour, the microporous separator membrane has a transverse-direction heat shrinkage of 1% or less at 120°C for 1 hour, and / or the microporous separator membrane is improved or modified using ionizing radiation energy.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to and the benefit of co-pending U.S. Provisional Patent Application Serial No. 62 / 145,549, filed April 10, 2015, which is hereby incorporated by reference in its entirety.

[0002] According to at least selected embodiments, the present application or invention is directed to new or improved separator membranes, separators, batteries incorporating such separators, methods of making such membranes and / or separators, and / or methods of using such membranes and / or separators. According to at least certain embodiments, the present invention is directed to ionizing radiation treated microporous polyolefin, polyethylene (PE), polypropylene (PP), copolymer and / or polymer blend (e.g., copolymers or blends including PE and other polymers such as polypropylene (PP)) membranes, microporous membranes, separator membranes, battery separators, and / or microporous battery separators for secondary or rechargeable lithium batteries, and / or ionizing radiation treated membranes, microporous membranes, separator membranes, battery separators, and / or or methods of making and / or using the microporous battery separator.

[0003] The microporous membrane or battery separator of the present invention can provide a lower onset temperature of thermal shutdown (or heat cutoff, hereinafter the same), can have an extended thermal shutdown window (or thermal shutdown window, hereinafter the same) where physical, dimensional and mechanical integrity is maintained at high temperatures, can have better oxidation resistance, can improve the battery safety performance of rechargeable lithium batteries, can provide a treated polyethylene, polypropylene or polyolefin separator membrane, can provide a treated dry process product with performance approaching or exceeding that of wet process products, can provide a treated polyethylene, polypropylene or polyolefin separator membrane with high temperature performance. and a polypropylene based separator membrane having the high temperature performance of a polypropylene based multi-layer or tri-layer product (by way of example only, a tri-layer membrane made from two polypropylene layers with a polypropylene or polyethylene layer in between, or a tri-layer membrane made from two polyethylene layers with a polypropylene or polyethylene layer in between) with reduced heat shrinkage resulting in both thermal stability and high temperature physical integrity that maintains separation of cathode and anode in battery systems, improves high temperature, high energy, high charge rate, and / or high voltage capabilities, improves safety, and / or provides a rechargeable or secondary lithium battery, and / or a combination thereof. This can be important to avoid short circuits or thermal runaway events during combination. [Background technology]

[0004] Ionizing radiation may include high speed, high energy, subatomic particles, ions or small atoms, and the like. Without wishing to be bound by theory, ionizing radiation may remove electrons from atoms or molecules as they pass through or collide with a material. The ionized atoms or molecules may undergo radiolysis, forming free radicals and inducing further chemical reactions. One form of ionizing radiation is electron beam or e-beam radiation. E-beam radiation can be of high (5-10 MeV), medium (500 keV-5 MeV) or low (80-500 keV) energy levels.

[0005] It may be desirable to modify the properties of various polymeric materials, improve the mechanical, thermal, and / or chemical properties of the polymer, and expand the range of applications of the polymer. The level of radiation dose can be significant in modifying and improving the mechanical, thermal and / or chemical performance properties of polymers such as polyolefins commonly used in microporous polyolefin battery separator membranes for rechargeable batteries such as various lithium batteries, such as lithium metal and / or lithium ion batteries.

[0006] Polyolefins, such as polyethylene (PE) and polypropylene (PP), are semi-crystalline polymeric materials commonly used in the fabrication of microporous separator membranes for use as battery separators in rechargeable lithium batteries. Without being bound by theory, e-beam irradiation of polyolefin materials forms free radicals that can break C-C (4.25 eV) and C-H (3.60 eV) bonds and induce the competing processes of chain scission versus crosslinking. The dominance of chain scission versus crosslinking is determined by the molecular weight, stereoregularity and crystallinity of the polymer, as well as the e-beam processing conditions, such as pressure, temperature, inert atmosphere and electron dose.

[0007] Figure 1 shows a semi-crystalline polymer consisting of amorphous and crystalline regions, where the polymer chains in the amorphous regions appear as loosely spirally wound chains that link together stacks of lamellae in the crystalline regions of the polymer. While chain scission predominates in the crystalline regions due to the lack of free radical mobility, crosslinking predominates in the amorphous regions due to the entanglement of the polymer chains. Crosslinked polymer chains are shown in both Figures 1 and 2. Due to the increase in molecular weight and the 3D network created by the crosslinks, crosslinked polymer materials tend to have high viscosity and high mechanical strength at high temperatures.

[0008] The polymeric materials can be used in microporous battery separator membranes. The battery separator includes a microporous membrane disposed between the cathode and anode in a battery system to prevent physical contact between the cathode and anode while allowing field ion flow during the charge and discharge cycles of the battery. There is an increasing demand for high energy density secondary lithium batteries (e.g., in some cases, lithium ion batteries).

[0009] There is an increasing demand for high energy lithium batteries for consumer electronics applications such as smart phones and laptop computers, for power tools, and for electric / hybrid electric vehicle applications. Such rechargeable, or secondary, lithium batteries include lithium ion batteries. Lithium ion batteries may include high performance microporous separator membranes. Summary of the Invention

[0010] According to at least selected embodiments, the present application or invention may address the above needs or demands and / or is directed to new or improved membranes, separator membranes, separators, batteries incorporating such separators, methods of making such membranes and / or separators, and / or methods of using such membranes and / or separators. According to at least certain embodiments, the present invention is directed to ionizing radiation treated polyolefin, polyethylene (PE), copolymers and / or polymer blends (e.g., copolymers or blends including PE and other polymers such as polypropylene (PP)) battery separators for secondary or rechargeable lithium batteries, and / or methods of making ionizing radiation treated microporous membrane battery separators.

[0011] According to at least selected embodiments, aspects or objectives, the present application or invention may provide or is directed to new or improved separator membranes, separators, batteries incorporating such separators, methods of making such membranes and / or separators, and / or methods of using such membranes and / or separators. According to at least one embodiment, the present invention provides ionizing radiation treated microporous polyolefin, polyethylene (PE), polypropylene (PP), copolymer and / or polymer blend (e.g., copolymers or blends including PE and other polymers such as polypropylene (PP)) membranes, microporous Porous membranes, separator membranes, battery separators, and / or microporous battery separators for secondary batteries or rechargeable lithium batteries, and / or ionizing radiation treated membranes, microporous membranes, Methods for making and / or using separator membranes, battery separators, and / or microporous battery separators are directed.

[0012] The microporous membrane or battery separator of the present invention can provide a lower onset temperature of thermal shutdown, can have an extended thermal shutdown window where physical, dimensional and mechanical integrity are maintained at elevated temperatures, can have better oxidation resistance, can improve battery safety performance of rechargeable lithium batteries, can provide a treated polyethylene, polypropylene or polyolefin separator membrane, can provide a treated dry process product that approaches, matches or exceeds the performance of wet process products, can provide a treated polyethylene, polypropylene or polyolefin separator membrane with higher temperature performance, can provide a treated dry process product with the high temperature performance of polypropylene based products. A treated polyethylene separator membrane can be provided, which has the high temperature performance of a polypropylene based multi-layer or tri-layer product (e.g., a tri-layer membrane made of two polypropylene layers with a polyethylene or polypropylene layer in between, or a tri-layer membrane made of two polyethylene layers with a polypropylene or polyethylene layer in between), can have reduced heat shrinkage, and provides both thermal stability and high temperature physical integrity that are important for maintaining separation of the cathode and anode in a battery system, improving high temperature, high energy, high charge rate, and / or high voltage capability, improving safety, and / or avoiding short circuits or thermal runaway events in rechargeable or secondary lithium batteries, or combinations thereof.

[0013] The microporous membranes, or battery separators of the invention can preferably provide a low onset temperature of thermal shutdown, have an expanded thermal shutdown window that maintains physical, dimensional, and mechanical integrity at elevated temperatures, can improve battery safety performance in rechargeable lithium batteries, can provide treated polyethylene separator membranes with the high temperature performance of polypropylene based tri-layer products (by way of example only, a tri-layer membrane made of two polypropylene layers with polyethylene in between), and can have reduced heat shrinkage, resulting in both improved thermal stability and high temperature physical integrity, which is important for maintaining separation of the cathode and anode of a battery system and avoiding thermal runaway events in rechargeable or secondary lithium batteries, and / or combinations thereof.

[0014] Ionizing radiation treatment of microporous polyethylene battery separators provides an inventive method for lowering the onset temperature of thermal shutdown. Additionally, the microporous polyethylene battery separator membranes treated with ionizing radiation have an extended thermal shutdown window, where the physical, dimensional and mechanical integrity of the microporous separator membrane is maintained at higher temperatures. The extended high temperature dimensional integrity of the inventive ionizing radiation treated separator membranes improves the battery safety performance of rechargeable lithium ion batteries. Additionally, the extended high temperature dimensional integrity of the inventive ionizing radiation treated separator membranes approaches the high temperature performance of polypropylene-based tri-layer products (by way of example only, a tri-layer membrane consisting of two polypropylene layers with a polyethylene layer in between). Additionally, the inventive battery separator membranes provide both improved thermal stability and high temperature physical integrity, which may be important for reducing thermal shrinkage, maintaining the separation of the cathode and anode in a battery system, and avoiding thermal runaway events in rechargeable or secondary lithium batteries.

[0015] Preferred thermal shutdown characteristics are a low onset temperature, a fast shutdown speed, and a sustained thermal shutdown window. Various separators that can have thermal shutdown characteristics can include, but are not limited to, a single layer polyethylene film, or a tri-layer of polypropylene and polyethylene. Down can be provided by polyethylene due to its low melting point of 130-140° C. As disclosed herein, electron beam radiation can provide a means to improve and custom modify the thermal, mechanical and / or chemical properties of microporous battery separator membranes using an economical, acceptable, clean and fast method.

[0016] There is an increasing demand for high energy or high voltage lithium batteries for consumer applications such as smart phones, laptop computers, power tools, and for electric / hybrid electric vehicles. Some such rechargeable secondary lithium batteries include lithium ion batteries. Lithium ion batteries include high performance microporous separator membranes. As described herein, electron beam radiation can provide a means to improve and customize the mechanical, thermal, and chemical properties of microporous battery separator membranes using a process that is economical, has excellent directionality in the direction of electron beam acceleration, and can be performed at high throughput rates.

[0017] Ionizing radiation treatment using electron beam (e-beam) radiation is a method for controlled and customized modification of the mechanical, thermal and / or chemical properties of microporous battery separator membranes to optimize the safety and / or performance of various batteries, such as rechargeable or secondary lithium batteries (by way of example only, lithium metal batteries, lithium ion batteries, etc.). The reduction in the thermal shrinkage of the microporous separator membranes results in increased levels of dimensional stability at elevated temperatures and improved safety performance in lithium batteries. The very low or no thermal shrinkage of the separator membranes prevents physical contact between the cathode and anode, reducing the possibility of electronic shorting of the battery.

[0018] Repeated charge and discharge cycles can change the dimensions of some internal components within the battery. The battery assembly process can involve stacking of cathode / separator / anode in layers or can involve a full length of stacked cathode / separator / anode rolled in a roll cake type configuration. Physical and electrical insulation between the cathode and anode is provided by the separator. Shrinkage of the separator in the machine or cross direction can, in some cases, lead to contact between the cathode and anode, creating the potential for a short circuit or thermal runaway event.

[0019] Electron beam treatment of polyethylene (PE) microporous battery separator membranes can achieve a reduction in the thermal dimensional shrinkage of the membrane. Electron beam treatment can be performed on PE microporous battery separator membranes manufactured using wet or dry methods. Wet processes include the thermally induced phase separation process (or TIPS process), which typically involves melting and mixing the polymer and processing aids (and possibly other ingredients) to form a non-porous extrudate precursor membrane, followed by one or more uniaxial and biaxial stretching steps that may be followed or preceded by one or more extraction steps in any order or combination of steps. Electron beam treatment can be performed on the non-porous extrudate precursor membrane before or after stretching, before extraction or after extrusion, in any order, and on the final finished good product and any combination of these steps.

[0020] To improve battery safety, lithium battery manufacturers may use microporous battery separators with thermal shutdown capabilities where the pores of the separator close to prevent ion flow between the electrodes at a shutdown temperature. Without ion flow, the battery will not function. Electron beam irradiation treatment of a shut down microporous battery separator membrane may provide a means to adjust the onset temperature of thermal shutdown. Electron beam irradiation treatment of a shut down capable microporous battery separator membrane may provide a means to fine tune the onset temperature of thermal shutdown, adjusting the onset temperature to lower temperatures. A microporous battery separator membrane with a lower thermal shutdown temperature provides an impeded state of ion flow at lower temperatures.

[0021] Thermal shutdown can be measured using an electrical resistance test, which measures the electrical resistance of the separator membrane as a function of temperature. The electrical resistance (ER) is measured in Ohms·cm of a separator filled with electrolyte. 2 When thermal shutdown occurs in the battery separator membrane, ER is approximately 1,000 to 10,000 ohm cm. 2 When the separator membrane maintains this level of electrical resistance at temperatures above 180°C, it is called a sustained high temperature thermal shutdown. Reducing the thermal shutdown temperature and extending the duration of the shutdown temperature widens the sustained 'window' of thermal shutdown. A wide thermal shutdown window can improve battery safety by reducing the potential for a thermal runaway event, and the possibility of a fire or explosion.

[0022] Thermal shutdown occurs at or near the melting point of the polymer. Thermal shutdown of polyethylene microporous battery separator membranes occurs at the melting point of PE, which ranges from 130°C to 145°C, depending on the molecular weight of the PE. If the temperature of the battery increases to 150°C, thermal shutdown may be lost due to loss of integrity of the melting point of the particular PE separator membrane. The thermal shutdown window of polyethylene microporous battery separators is, in some cases, 5-15°C, which may be considered a narrow window. In a tri-layer microporous battery separator membrane containing polypropylene (PP) and polyethylene (PE), the polypropylene portion may melt at about 165°C.

[0023] Thermal shutdown of a polypropylene / polyethylene / polypropylene (PP / PE / PP) tri-layer battery separator membrane may, in some cases, have a thermal shutdown onset temperature of 135-145°C due to the PE layer, but does not melt sufficiently until 165°C due to the PP layer. A sustained thermal shutdown window may occur from 135-145°C to 165°C in some cases, continuing until the integrity of the PP layer is lost. Thus, in some cases, the thermal shutdown window of a PP / PE / PP tri-layer battery separator membrane may be wider than that of, for example, a mono-layer polyethylene separator, and therefore may have some desirable characteristics, such as good thermal performance in lithium rechargeable batteries.

[0024] With regard to thermal performance, it may be desirable to widen the thermal shutdown window for various PE microporous battery separators. Electron beam treatment of PE microporous battery separator membranes achieves lower shutdown initiation temperatures and higher melt integrity of the PE layer, producing the desired widened thermal shutdown window.

[0025] Electron beam treatment may have the additional benefit of improving electrolyte wetting of microporous battery separator membranes. Low e-beam irradiation of PE microporous battery separator membranes may alter the electrolyte wetting of lithium batteries by decreasing the contact angle of the electrolyte liquid both on the separator membrane surface and within the internal porous structure of the microporous separator membrane. Lower contact angles indicate higher electrolyte absorption which may lead to improved capacity of lithium batteries. [Brief description of the drawings]

[0026] [Figure 1] FIG. 1 includes a schematic diagram of a semi-crystalline polymer showing crystalline and amorphous regions before and after electron beam treatment. [Diagram 2] FIG. 2 includes schematic diagrams of cross-linked polymer chains before and after electron beam radiation treatment. [Diagram 3]Figure 3 contains the thermal shutdown curves as a function of electron beam processing dose for a 9 μm microporous polyethylene paraplate membrane. [Figure 4] Figure 4 contains the thermal shutdown curves as a function of electron beam treatment dose for the microporous separator membrane. [Diagram 5] FIG. 5 contains the MD heat shrinkage % after 1 hour at 105° C. as a function of electron beam treatment dose for 12 μm microporous polyethylene paraffin membranes. [Figure 6] FIG. 6 contains the MD heat shrinkage % after 1 hour at 120° C. as a function of electron beam treatment dose for 12 μm microporous polyethylene paraffin membranes. [Figure 7] FIG. 7 contains the TD heat shrinkage % after 1 hour at 105° C. as a function of electron beam treatment dose for 12 μm microporous polyethylene paraffin membranes.

[0027] [Figure 8] FIG. 8 contains the TD heat shrinkage % after 120° C. for 1 hour as a function of electron beam treatment dose for 12 μm microporous polyethylene paraffin membranes. [Figure 9] Figure 9 contains the thermal shutdown curves as a function of electron beam processing dose for a 12 μm microporous polyethylene paraplate membrane. [Figure 10] Figure 10 contains the thermal shutdown curves for untreated and E-beam treated microporous separator membranes. [Figure 11] FIG. 11 contains the TMA of untreated and E-beam treated 12 μm microporous polyethylene paraffin membranes. [Figure 12] FIG. 12 includes the hole size distribution of the electron beam treatment of Example 3 compared to Comparative Example 1. [Figure 13] FIG. 13 includes the hole size distribution of the electron beam treatment of Example 7 compared to Comparative Example 2. [Figure 14] FIG. 14 includes an SEM micrograph of the Comparative Example 2 surface prior to electron beam treatment.

[0028] [Figure 15] FIG. 15 includes an SEM micrograph of the Example 7 surface after electron beam treatment. [Figure 16] FIG. 16 includes overcharge test plots for the non-radiation treated Comparative Example 1. [Figure 17] FIG. 17 contains the overcharge test plots for E-beam treated Example 3. [Figure 18] FIG. 18 includes a photograph of the inventive separator membrane Example 3 after autopsy of the hot box test cell, showing that the separator was intact after being peeled off from the negative electrode. [Figure 19] FIG. 19 includes a photograph of Comparative Example 1 after autopsy of the hot box test cell showing that the separator had melted to the negative electrode and could not be peeled off from the negative electrode. [Figure 20] FIG. 20 includes the results of ball crush testing of Comparative Example 1. [Figure 21] FIG. 21 contains the results of ball crush testing on Example 3. [Figure 22] FIG. 22 contains the cycling performance test results for the 9 μm polyethylene microporous separator membrane. BEST MODE FOR CARRYING OUT THEINVENTION

[0029] According to at least selected embodiments, the present application or invention is directed to new or improved separator membranes, separators, batteries incorporating such separators, methods of making such membranes and / or separators, and / or methods of using such membranes and / or separators. According to at least one particular embodiment, the present invention is directed to ionizing radiation treated microporous polyolefin, polyethylene (PE), copolymers and / or polymer blends (e.g., copolymers or blends including PE and other polymers such as polypropylene (PP)) battery separators for secondary or rechargeable lithium batteries, and / or methods of making ionizing radiation treated microporous battery separators. In various embodiments in which a blend or copolymer including PE is used, such blend or copolymer may include, for example, about 90% or more PE, or about 95% or more PE, etc.

[0030] The microporous membrane or battery separator of the present invention preferably provides a lower onset temperature of thermal shutdown, has an extended thermal shutdown window where physical, dimensional, and mechanical integrity are maintained at elevated temperatures, can improve battery safety performance in rechargeable lithium batteries, can provide a treated polyethylene separator membrane with the high temperature performance of polypropylene based tri-layer products (by way of example only, a tri-layer membrane consisting of two polypropylene layers with a polyethylene layer between), can reduce heat shrinkage and maintain separation of cathode and anode in battery systems, and can be used in rechargeable or secondary batteries. It may provide both thermal stability and high temperature physical integrity, which are important for avoiding thermal runaway events in lithium batteries, and / or combinations thereof.

[0031] Ionizing radiation treatment of microporous polyethylene battery separators provides a method to reduce the onset temperature of thermal shutdown. Additionally, microporous polyethylene battery separator membranes treated with ionizing radiation have an extended thermal shutdown window, where the physical, dimensional and mechanical integrity of the microporous separator membrane is maintained at higher temperatures. The extended high temperature dimensional integrity of the ionizing radiation treated separator membranes of the present invention improves the battery safety performance of rechargeable lithium ion batteries. Additionally, the extended high temperature dimensional integrity of the ionizing radiation treated separator membranes of the present invention approaches the high temperature performance of polypropylene based tri-layer products (as an example only, a tri-layer membrane made from two polypropylene layers with a polyethylene layer in between). Additionally, the battery separator membranes of the present invention can provide both thermal stability and high temperature physical integrity, which are important for reducing thermal shrinkage, maintaining the separation of the cathode and anode in a battery system, and avoiding thermal runaway events in rechargeable or secondary lithium batteries.

[0032] Ionizing radiation treatment in the form of electron beam radiation may provide a method or means to control and modify the thermal, mechanical and / or chemical properties or aspects of a microporous battery separator membrane to optimize its safety and / or performance in various secondary or rechargeable lithium batteries. In various embodiments described herein, e-beam radiation may be performed alone on the separator membrane or may be performed before, after, or simultaneously with other treatments such as heat treatment, IR treatment, other chemical cross-linking treatments, etc.

[0033] Rechargeable lithium battery manufacturers often require thin microporous separator membranes with thicknesses of 6-20 μm (sometimes even thinner), more preferably in the range of 8-16 μm thick, and most preferably in the range of 8-14 μm thick. Lithium battery manufacturers place great emphasis on the safety performance of lithium batteries and believe that the battery separator membrane plays a key role in the energy density, cycle life and safety of the battery.

[0034] Thin separators are preferred by battery manufacturers striving to produce high energy density lithium batteries, e.g., lithium-ion batteries, with low weight. The thinner the separator membrane, the more electrode / separator sandwiches can be packed into a battery cell, resulting in high energy density. However, thin battery separators with thicknesses less than 14 μm should be dimensionally stable in both the machine direction (MD) and transverse direction (TD) at high temperatures and should also have low thermal MD and TD shrinkage to maintain physical separation between the battery's anode and cathode during the battery's charge and discharge cycles.

[0035] Repeated charge and discharge cycles cause changes in the dimensions of battery separator membranes throughout the life of the battery. The battery assembly process involves the length of a cathode / separator / anode stack, or a stacked cathode / separator / anode sandwich-like structure rolled in a roll-cake type configuration. The separator provides physical and electrical insulation between the cathode and anode. Shrinkage in the machine or cross direction of the separator can lead to contact between the cathode and anode, creating the potential for a short circuit or thermal runaway event, and the potential for battery fire or explosion.

[0036] Monolayer and multilayer polyethylene microporous separator membranes can be treated with electron beam radiation to modify their thermomechanical performance properties to improve safety performance in lithium batteries (examples include monolayer and multilayer membranes, copolymer membranes, polymer blend membranes). The dose range of electron beam irradiation depends on the molecular weight of the polymer, the crystallinity / amorphous content of the polymer, the process conditions of the equipment, the chemistry of the gas atmosphere exposure before and during processing, the thickness of the film being processed, and the desired separator thickness. The performance of the data membrane will depend on several factors, including the chemical, mechanical and thermal performance properties of the membrane. In various embodiments described herein, the polymer used can be polyethylene having a molecular weight of less than about 800,000. In some embodiments, the polyethylene is It is high density polyethylene.

[0037] Semicrystalline polymers consist of amorphous regions and crystalline regions where polymer chains in the amorphous regions connect with lamellar stacks in the crystalline regions of the polymer. The amount of crystalline regions is indicated by the degree of crystallinity or percent crystallinity. The crystallinity of polyolefins can be affected by exposure to electron beam radiation because the electron beam can break chemical bonds through chain scission, producing shorter polymer chains. Electron beam treatment can also produce free radical species that can produce crosslinking reactions between polymer chains, making longer polymer chains or creating a network of chemically bonded polymer chains, as shown in Figure 2.

[0038] The dominance of chain scission versus crosslinking activity is balanced by selecting parameters such as the type of polymer, its molecular weight and distribution, crystallinity, amorphous content, and stereoregularity, and by selecting the electron beam treatment conditions such as pressure, temperature, the presence of oxygen in the selected gas atmosphere, and electron beam dose. Many polymers undergo both crosslinking and scission, and the dominance of these processes depends on the chemical structure and morphology of the polymer, as well as the selected electron beam treatment conditions.

[0039] Battery manufacturers use very thin microporous separator membranes ranging from 8-20 μm thick, more preferably 8-16 μm thick, and most preferably 8-14 μm thick, because the thinner the separator membrane, the more electrode material can be designed into the battery cell due to the increasing demand for high energy batteries such as lithium ion batteries. Thinner separator membranes have less polymer per unit volume and therefore, in some cases, may have weaker mechanical strength in the two dimensional XY directions, the machine direction and the transverse direction, than thicker separators. Because thinner separator membranes have less polymer per unit volume, in some cases, they may be weaker in the “Z” direction, as measured by puncture strength, than thicker separators. E-beam processing may be used to improve the high temperature mechanical strength of separator membranes in the X, Y, and Z directions by chemically and permanently modifying the length of the polymer chains, the amount of interpolymer bonds between the chains, and the entanglement of the polymer chains.

[0040] Electron beam irradiation of polymeric materials can lead to the generation of free radicals. The free radicals can lead to decomposition and / or crosslinking phenomena in the polymeric material. The predominance of free radical generation with chain degradation versus the occurrence of crosslinking leading to chain extension as a result of e-beam treatment is influenced by the amount of crystalline and amorphous regions in the polymer. E-beam treatment affects the amorphous regions of the polymer by the formation of interpolymer bonds known as crosslinks. Figure 1 shows the results of e-beam irradiation on a polymer. E-beam treatment can affect the crystalline regions of the polymer by chain scission generating free radicals on the more available parts of the polymer chains, for example on one or more outer bends of the polymer chains in folded lamellar crystalline regions.

[0041] E-beam (or e-beam) treatment of polyethylene separator membranes can affect some of the mechanical strength properties depending on the choice of electron beam dose. Mechanical properties such as MD and TD tensile strength, tensile strain and Young's modulus of the separator membranes of the present invention are not adversely affected by e-beam treatment of 9 μm and 12 μm microporous separator membranes for process conditions determined in many experimental efforts. Furthermore, the dielectric breakdown, microindentation and mixed infiltration of e-beam treated PE microporous separator membranes are not adversely affected. Thermomechanical analysis (TMA) shows that when performed in tension mode where test samples are held under constant tension and the temperature is increased from room temperature to elevated temperatures, the thermal rupture temperature shifts to higher temperatures (Figure 1). 11).

[0042] The thermal burst temperature is the temperature at which the membrane breaks under applied tension as the temperature is increased. The effect of crosslinking as a result of e-beam treatment of the microporous PE separator membrane causes this upward shift in the burst temperature, demonstrating that the e-beam treated membrane does not break as easily under tension at higher temperatures. The rate of dimensional change after an electron beam dose of 100 kGy is not as rapid. E-beam treatment provides a way to fine-tune the thermal burst temperature of the PE microporous separator membrane by shifting it higher or lower depending on the desired thermal performance of the battery, such as a lithium-ion battery.

[0043] Thermal shutdown occurs at the temperature at which the pores in the microporous separator membrane close and the separator membrane can no longer conduct ions. Thermal shutdown in polyethylene microporous battery separator membranes occurs at or near the melting point of the polymer, which is typically in the range of 130-145 °C, depending on the molecular weight, density, stereoregularity and crystallinity of the PE. When thermal shutdown occurs in a battery separator membrane, the electrical resistivity (ER) drops to approximately 1,000-10,000 ohm cm. 2 When the separator membrane reaches a high level of resistance, the battery is said to be in a "shutdown" state. If the separator membrane maintains this level of electrical resistance at temperatures ≥ 180°C, this is called a sustained high temperature thermal shutdown.

[0044] For polyethylene microporous separator membranes, the temperature of the battery may continue to rise even after the battery temperature reaches 130-145°C and thermal shutdown occurs. At temperatures of 150°C, in some cases, thermal shutdown may be lost due to loss of 'melt integrity' of the polyethylene separator membrane. Melt integrity refers to the physical structure of the membrane, defined by the dimensions where the membrane has softened but retained its shape. Loss of melt integrity means that the membrane no longer retains its shape and is fluid. From a battery safety perspective, it is desirable for the microporous separator membrane to maintain its physical shape at high temperatures and have high temperature melt integrity (HTMI).

[0045] The electron beam treated polyethylene microporous separator membrane of Example 3 in Figure 3 has a thermal shutdown window that extends from about 137.5 °C to 180 °C, with thermal shutdown initiation occurring at a temperature of 10 ohms cm. 2 to 10,000 ohm cm 2 The ER rises sharply above 0.05%, indicating that the pores in the separator membrane are closed by melting of the polymer, blocking the flow of ions through the battery. If the physical integrity of the membrane is maintained and the ER remains high, the battery separator provides a physical barrier separating the anode from the cathode, preventing the opportunity for a thermal runaway event to occur.

[0046] A typical polyethylene microporous battery separator with a thickness of about 25 μm or less has a thermal shutdown window of the order of 5-15°C, sometimes even lower (e.g., a total shutdown window of about 144-147°C of 3°C). This is considered a narrow thermal shutdown window. One possible means of increasing the thermal shutdown window is to incorporate a higher melting temperature polymer into the PE. Another way to extend the thermal shutdown window of a porous separator membrane is to layer the PE with one or more higher melting temperature porous layers, such as a polypropylene porous membrane layer. The thermal shutdown window can also be tailored by using polypropylene (PP), for example, in a 'polypropylene / polyethylene / polypropylene' three-layer separator configuration, where the inner polyethylene layer contributes to an early thermal shutdown of 130-145°C and the polypropylene outer layer contributes to a higher thermal shutdown around 165°C.

[0047] Polypropylene / Polyethylene / Polypropylene (PP / PE / PP) tri-layer battery separator The thermal shutdown of the PE membrane can have an onset temperature as low as 130°C because the PE inner layer is used to produce some wet process PE membranes or films. Because it can be manufactured using a dry process, a lower molecular weight PE can be used than the PE used. Comparative Example 4 in Figure 4 is a PP / PE / PP membrane with a shutdown onset temperature of 130.5°C and a sustained thermal shutdown window that extends to about 180°C. The thermal shutdown window of the polypropylene-containing tri-layer battery separator membrane is wider than that of the non-radiated PE separator membrane, imparting good thermal safety performance to lithium-ion rechargeable batteries at high temperatures.

[0048] The method of the present invention uses low energy electron beam radiation to modify PE microporous battery separator membranes to produce thermally stable PE microporous battery separator membranes that can compete with trilayer PP / PE / PP microporous battery separator membranes for high temperature performance. PE microporous battery separator membranes treated with low energy e-beam radiation can achieve lower onset shutdown temperatures and higher melt integrity, resulting in the desired extended thermal shutdown window similar to PP-containing membranes. In various embodiments described herein, the shutdown window can be increased from a narrow range (e.g., a total window of about 3 to about 15°C) to a window of more than about 30°C (e.g., the onset temperature of shutdown is extended to less than about 138°C, e.g., 137°C, where shutdown is sustained to above 170°C). Electron beam treatment of PE microporous separator membranes closes the gap in high temperature performance between PE and PP in battery separator membranes for lithium ion batteries, performing similarly to PP-containing membranes. EXAMPLES

[0049] Single-layer polyethylene microporous separator membranes were treated with electron beam radiation to modify thermal and mechanical performance properties and improve safety performance in lithium-ion batteries. Ionizing radiation treatment using electron beam radiation is a promising innovative approach to controllable modification of the mechanical, thermal and chemical properties of microporous battery separator membranes to optimize safety performance in lithium-ion batteries. Electron beam irradiation of very thin microporous separator membranes with thicknesses less than 14 μm produced separator membranes with reduced thermal shrinkage at high temperatures and high levels of dimensional stability, resulting in improved safety performance in lithium-ion batteries.

[0050] A very low or zero thermal shrinkage of the separator film prevents physical contact between the anode and cathode, reducing the chance of electrical shorting of the battery. In some cases, repeated charge-discharge cycles can cause slight changes in the dimensions of some internal components of the battery, including the separator film. The battery assembly process involves stacking cathode / separator / anode layers, or the entire length of laminated cathode / separator / anode rolled in a roll-cake configuration. Physical and electrical insulation between the cathode and anode is provided by the separator. The separator's machine or cross-machine shrinkage can lead to contact between the cathode and anode electrodes, creating the potential for shorting or thermal runaway, reducing the potential for battery fire or explosion.

[0051] Tables 1 and 2 below list performance data for various separator membranes having thicknesses ranging from about 9 μm and 12 μm, some of which were microporous separator membranes that were electron beam treated. The electron beam dose ranged from 70 to 120 kGy at an accelerating voltage of 180 kV. The line speed was 50 feet / min, and the films were processed in a nitrogen atmosphere with oxygen levels maintained below 10 ppm.

[0052] In Table 1, Patent Examples 1, 2 and 3 are examples of 9 μm (approximately 9 μm) wet-processed microporous monolayer polyethylene battery separator membranes of the present invention, which were treated with electron beam doses of 70, 80 and 90 kGy, respectively. Comparative Examples 1 and 5 are examples of electron beam doses of 70, 80 and 90 kGy, respectively. Comparative Example 4 is a 9 μm (approximately 9 μm) wet process microporous monolayer polyethylene battery separator membrane that is not e-beam treated. Comparative Example 5 is a 8.7 μm dry process polypropylene-containing PP / PE / PP trilayer microporous battery separator membrane that is not e-beam treated.

[0053] In Table 2, Patent Examples 4, 5, 6, 7 and 8 are examples of 12 μm wet process microporous monolayer polyethylene battery separator membranes of the present invention, which were treated with electron doses of 70, 80, 90, 100 and 120 kGy, respectively. Comparative Examples 2 and 6 are 12 μm and 13.5 μm wet process microporous monolayer polyethylene battery separator membranes, respectively, that were not electron beam treated. Comparative Example 3 is an example of a 12 μm wet process microporous monolayer polyethylene battery separator membrane that was not electron beam treated. It is a 14μm dry process polypropylene-containing PP / PE / PP tri-layer microporous battery separator membrane.

[0054] The method of the present invention using electron beam radiation to modify the thermal performance of PE microporous membranes achieved a reduction in machine direction (MD) and transverse direction (TD) shrinkage. Figure 5 shows the %MD heat shrinkage at 105°C for 1 hour for 12 μm microporous polyethylene separator membranes as a function of electron beam treatment dose. The electron beam dose levels range from 70 to 120 kGy. The %MD heat shrinkage level of the microporous polyethylene separator membranes treated with 120 kGy electron beam dose was reduced from 4% to 2%. Figure 6 shows the %MD heat shrinkage at 120°C for 1 hour for 12 μm microporous polyethylene separator membranes as a function of electron beam treatment dose. The %MD heat shrinkage level of the microporous polyethylene separator membranes treated with 120 kGy electron beam dose was reduced from 8% to 4.5%.

[0055] Figures 7 and 8 show the results of transverse direction (TD) heat shrinkage tests of e-beam treated PE separator membranes at e-beam doses ranging from 70 kGy to 120 kGy. The %TD heat shrinkage was reduced to nearly 0 at 120°C.

[0056] [Table 1]

[0057] [Table 2]

[0058] In addition to reducing the thermal shrinkage, e-beam radiation affects the onset temperature of thermal shutdown. Figure 3 shows the thermal shutdown curve of a 9 μm microporous PE separator membrane as a function of e-beam dose. The onset temperature of thermal shutdown is observed to decrease from approximately 143°C to 139°C.

[0059] Electron beam radiation is a type of ionizing radiation in which accelerated electrons have enough energy to break chemical bonds in polymers. Common types of chemical processes are chain scission and crosslinking. These processes can occur simultaneously when a polymer is irradiated with a low-energy electron beam. Chain scission occurs when the electron beam breaks chemical bonds and generates one or more free radicals that can lead to shortened polymer chains or fragments. At the same time, the low-energy electron beam can generate free radicals along the polymer chain or at the end of the polymer chain that generate sites for crosslinking reactions. Figure 2 shows a schematic diagram of various polymer chains that have been crosslinked using electron beam radiation to chemically bond one or more polymer chains together.

[0060] The e-beam treated PE microporous separator membranes of the present invention have a lower onset of thermal shutdown than untreated PE separator membranes. The lower onset temperature of thermal shutdown in the separator has an improved level of safety compared to separators with higher thermal shutdown temperatures. The lower temperature of thermal shutdown can be predominantly attributed to chain scission, while the enlarged and widened thermal shutdown window can be primarily due to crosslinking. The dominance of chain scission versus crosslinking activity can be balanced by selecting parameters such as the type of polymer, its molecular weight and distribution, crystallinity, amorphous content, and stereoregularity, and by selecting the e-beam processing conditions, such as pressure, temperature, presence of oxygen in the gas atmosphere, and dose of the e-beam. The dose of the electron beam ranged from 70 to 120 kGy at an accelerating voltage of 180 kV. The line speed was 50 feet / min, and the films were processed in a nitrogen atmosphere with oxygen levels maintained below 10 ppm. Many polymers undergo both crosslinking and scission, and the process that prevails depends on the chemical structure and morphology of the polymer, as well as the e-beam processing conditions selected.

[0061] Thermal shutdown of polyethylene microporous battery separator membranes may depend on the molecular weight and crystallinity of the PE and occurs at or near the melting point of the polymer, which is typically in the range of 130-145 °C. When thermal shutdown occurs in a battery separator membrane, the electrical resistivity (ER) drops to approximately 1,000-10,000 ohm cm. 2 When the separator membrane reaches a high ionic resistance level of the order of 1000-10,000 ohm cm at temperatures above 180°C, the separator membrane is said to 'shut down'. 2 If the temperature remains above this level, this is called a 'sustained high temperature thermal shutdown'.

[0062] For polyethylene microporous battery separator membranes, when the battery temperature increases to 150°C, in some cases, thermal shutdown may be lost due to loss of melt integrity of the polyethylene separator membrane. The thermal shutdown window for polyethylene microporous battery separators is on the order of 5-15°C, which is considered a narrow thermal shutdown window. The thermal shutdown window can be adjusted by combining polyethylene with a higher melting temperature polymer, such as polypropylene, by blending PE with PP. However, PP has low compatibility with PE, and the two polymers tend not to mix well. Another way to incorporate PP and PE into a separator is by laminating one or more layers of PP with one or more layers of PE to create a stacked laminated membrane.

[0063] The preferred configuration for the separator containing laminated PP and PE is a 'polypropylene / polyethylene / polypropylene' three-layer separator membrane configuration, with the inner polyethylene layer contributing to early thermal shutdown at about 130-135°C and the polypropylene outer layer contributing to early thermal shutdown at about 16°C. This contributes to a higher thermal shutdown at 5°C. The thermal shutdown of polypropylene / polyethylene / polypropylene (PP / PE / PP) trilayer battery separator membranes is For example, a dry process may have an onset thermal shutdown of 130°C in some cases due to an inner PE layer, but may not melt completely until 165°C due to the PP layer.

[0064] FIG. 4 includes the thermal shutdown curves of the PP-containing membrane Comparative Example 4, a PP / PE / PP separator membrane. The sustained thermal shutdown window of Comparative Example 4 occurs at 130.5° C. and continues until loss of integrity of the PP layer above 180° C. The thermal shutdown window of the PP / PE / PP tri-layer battery separator membrane is wider than the non-irradiated PE separator membrane Comparative Example 1. The PP-containing Comparative Example 4 tri-layer battery separator membrane has good thermal performance in lithium-ion rechargeable batteries.

[0065] For PE microporous battery separator membranes to compete with trilayer PP / PE / PP microporous battery separator membranes in terms of thermal performance, the PE thermal shutdown window needs to be extended. Electron beam treatment of PE microporous battery separator membranes achieves a low shutdown onset temperature and produces a higher melt integrity PE layer with the desired extended thermal shutdown window similar to PP-containing membranes. Electron-treated PE microporous battery separator membranes have a wide thermal shutdown window and maintain high temperature melt integrity up to temperatures above 180°C, similar to PP-containing battery separator membranes in rechargeable lithium ion batteries.

[0066] Figure 3 shows the thermal shutdown curves for 9 μm separator membranes treated with e-beam radiation ranging from 70 to 90 kGy. Example 1, Example 2 and Example 3 were treated with e-beam doses of 70, 80 and 90 kGy, respectively. The onset temperature of thermal shutdown decreased from approximately 142°C to 137.5°C as the e-beam dose increased. As the e-beam dose increases, the thermal shutdown window is widened. Figure 4 shows that the thermal shutdown window of Example 3 extends to about 180°C, similar to that of the PP-containing trilayer PP / PE / PP separator membrane Comparative Example 4. Figure 9 shows the thermal shutdown curves for various 12 μm thick PE microporous separator membranes with e-beam doses ranging from 70 to 120 kGy. As the e-beam dose increases, the thermal shutdown window of the 12 μm separator membrane is widened at high temperatures.

[0067] Example 8 was treated with an e-beam dose of 120 kGy and has a wide thermal shutdown window spanning over 180° C. FIG. 10 shows the thermal shutdown curves of Example 8 and Comparative Example 2, the latter of which is a PE separator membrane that was not e-beam treated. The beneficial effect of e-beam treatment is shown by comparing Example 8 and Comparative Example 2, where Comparative Example 2 has a very narrow thermal window of about 5° C., while Example 8 has an expanded thermal shutdown window similar to that of the PP / PE / PP tri-laminate separator membrane of Comparative Example 3, indicating that e-beam treatment produced a PE membrane with a thermal shutdown window similar to that of membranes containing one or more PP layers.

[0068] The inventive e-beam treatment for PE microporous separator membranes demonstrates the importance of lowering the onset temperature of thermal shutdown and extending the thermal shutdown window beyond 180°C. E-beam treatment of microporous separator membranes produces separator membranes of higher melt integrity with improved levels of safety performance in rechargeable lithium ion batteries.

[0069] The effect of low energy electron beam treatment on the mechanical strength of separator membranes was investigated using thermomechanical analysis (TMA), which measures the mechanical strength of the membrane as a function of temperature. When TMA is performed in 'tensile' mode, the test sample is held under constant tension while the temperature is increased from room temperature to an elevated temperature. TMA testing of e-beam treated PE microporous membranes was performed to measure the thermal burst temperature. The untreated Comparative Example 2 exhibits a rapid melting at around 141° C. and undergoes a rapid change in physical dimensions.

[0070] The e-beam treated samples, Example 6 and Example 7, were treated at 90 and 100 kGy, respectively, and responded to the applied stress in different ways. Example 6 and Example 7 showed a slower rate of dimensional change as the temperature increased, indicating that the membranes were more resistant to dimensional changes due to e-beam treatment. It is believed that the increase in strength may be due to the occurrence of crosslinking in the PE polymer membrane, and the upward shift in burst temperature may indicate that the membrane is stronger near its melting temperature.

[0071] E-beam processing offers a way to fine-tune the thermal burst temperature of the PE microporous separator membrane by moving it higher or lower depending on the desired thermal performance. The increased high temperature melt strength can help maintain separation of the cathode and anode in the event of a thermal runaway event.

[0072] The effect of electron beam radiation on the pore size distribution of microporous PE separator membrane is shown in Figure 12 and Figure 13. There is no statistical difference in the pore size distribution resulting from e-beam treatment for both 9μm and 12μm PE microporous separator membrane. Table 3 shows the percentage of porosity data, indicating that e-beam radiation does not affect the porosity of the microporous separator membrane.

[0073] [Table 3]

[0074] The surface morphology of the e-beam treated PE microporous separator membrane is shown in the scanning electron micrographs presented in Figure 15. The low energy e-beam treatment did not damage the membrane's surface or pores (see also Figure 14, which depicts an untreated membrane). The e-beam treatment was performed at low e-beam dose levels, and no degradation was observed on the surface or internal pore structure of the PE microporous separator membrane.

[0075] Electron beam treatment has the additional benefit of improving electrolyte wetting of microporous battery separator membranes. Low e-beam irradiation of PE microporous battery separator membranes can change electrolyte wetting in lithium ion batteries by decreasing the contact angle of the electrolyte on both the surface of the separator membrane and throughout the internal pore structure of the microporous separator membrane. A lower contact angle indicates higher electrolyte absorption, which can lead to improved capacity of lithium ion batteries. Table 4 lists the contact angle measurement results of 9 μm PE microporous separator membranes. When the contact angle with the electrolyte propylene carbonate on the surface was exposed to e-beam radiation at a dose of 90 kGy, the contact angle decreased from 75.8° to 60.2°, which is a 20% decrease.

[0076] [Table 4]

[0077] Overcharge, cycling, hot box and ball crush safety tests were performed on battery cells containing the e-beam treated PE microporous membrane of the present invention. During the overcharge test performed with the e-beam radiated membrane, the fully charged cell is subjected to a charge rate of 3C at 5V. The requirement for passing the overcharge test is that there is no explosion or fire in the battery. The overcharge test results of Comparative Example 1 and Example 3 are shown in Figures 16 and 17, respectively, and show that the residual current during overcharge after shutdown for Example 3 is lower compared to the non-e-beam radiated membrane Comparative Example 1, which is an improvement in overcharge performance.

[0078] Example 3 was subjected to hot box testing at 150°C for 1 hour. The battery cell was cooled and opened to observe the appearance of the e-beam treated film after hot box testing. Figure 18 is a photograph of Example 3 after removal from the prismatic battery. The e-beam treated Example 3 peeled away from the cathode in an intact piece, indicating that it had not lost its fusion integrity and maintained its physical dimensions. In contrast, Figure 19 shows that the untreated PE film Comparative Example 1 was completely attached to the cathode. Comparative Example 1 could not be separated or peeled away from the cathode, indicating that the untreated PE film had melted to the cathode as a result of the high temperatures experienced during the hot box testing.

[0079] The results of the ball crush test, plotted as a function of time while temperature and voltage were measured, are shown in Figures 20 and 21. The ball crush test is a type of internal short circuit test in which a spherical probe is pressed against the exterior surface of the battery cell and an increasing load is applied. Both samples passed the ball crush test, indicating that the e-beam treatment did not adversely affect the safety performance of the PE microporous separator membrane in lithium-ion batteries.

[0080] The results of the battery cycling test are shown in FIG. 22, and Example 3 has a higher capacity than Comparative Example 1, which can be attributed to the increased electrolyte absorption as a result of the e-beam treatment. During e-beam treatment, polyethylene undergoes a series of chemical reactions, including oxidation, resulting in a reaction at 1720 cm -1 The carbonyl groups can make the polyethylene more hydrophilic, which can lead to the PE membrane absorbing more electrolyte and resulting in higher capacity. Example 3 has been cycled for about 200 times and shows a higher capacity than the consistent non-irradiated Comparative Example 1.

[0081] Test Method Thickness Thickness is measured using an Emveco Microgage 210-A precision micrometer thickness tester per test method ASTM D374. Thickness values ​​are reported in microns, μm.

[0082] Puncture strength Test samples are first preconditioned at 73.4°C and 50% relative humidity for a minimum of 20 minutes. An Instron Model 4442 is used to measure the puncture strength of the test samples according to ASTM D3763. Thirty diagonal passes are performed on a 11 / 4" x 40" continuous specimen. The needle has a radius of 0.5 mm. The descent speed is 25 mm / min. The film is held tightly in a clamping fixture which utilizes an O-ring to hold the test sample firmly in place. The diameter of this clamped area is 25 mm. The displacement (mm) of the film punctured by the needle is recorded against the resistance force (gram force) exerted by the tested film. The maximum resistance force is the puncture strength in grams force (gf). A load-displacement plot is produced by this test method.

[0083] Pore ​​size distribution Pore ​​size is measured using an Aquapore Porosimeter available through Porous Materials, Inc. (PMI). Pore size is reported in μm.

[0084] porosity The porosity of the microporous film samples was measured using ASTM method D-2873 and is defined as the void space percent of the microporous membrane.

[0085] TD and MD tensile strength Tensile strength is measured along the machine direction (MD) and transverse direction (TD) using an Instron Model 4201 according to ASTM D-882 method.

[0086] Electrical Resistivity (ER) (also known as Ionic Resistance, IR) The electrical resistance, in ohms cm, of the electrolyte-filled separator 2 The unit of electrical resistance is ohm cm. 2 The separator resistance is characterized by cutting small pieces of separator from the finished material and then placing them between two blocking electrodes. The separator is saturated with battery electrolyte with 1.0 M LiPF6 salt in EC / EMC solvent in a volume ratio of 3:7. The resistance (R) in ohms (Ω) of the separator is measured by a four-probe AC ​​impedance technique. To reduce the measurement error at the electrode / separator interface, a large number of measurements are required by adding more layers. Based on the measurements of a large number of layers, the electrical (ionic) resistance R of the separator saturated with electrolyte is s (Ω) is the formula R s =p s Calculated by l / A, p s is the ionic resistivity of the separator in Ω-cm, and A is c m 2 is the electrode area in units and l is the separator thickness in cm. s / A is the slope calculated for the change in separator resistance (ΔR) for multiple layers (Δδ), which is expressed as ΔR / Δδ.

[0087] Heat shrinkage rate Shrinkage testing is measured by placing a 10 cm x 10 cm membrane sample in a manila folder, which is then hung in an oven using clips. Shrinkage was measured using calipers in MD and TD before and after placing a test sample in an oven at 105°C for 1 hour. Shrinkage was also measured using calipers in MD and TD before and after placing a second test sample in an oven at 120°C for 1 hour. Shrinkage is expressed as %MD shrinkage and %TD shrinkage using a modified ASTM 2732-96.

[0088] Dielectric Breakdown (DB) Dielectric breakdown (DB) is a measurement of the electrical insulation of the separator. A voltage is applied to the separator film at a ramp rate of 6,000 V / sec until dielectric breakdown of the sample is observed. A high DB indicates that the separator will have good winding yield and low HiPot failure rate.

[0089] Hot Electrical Resistance (ER) Hot electrical resistance is a measure of the resistance of a separator film under 50 pounds of pressure while the temperature is increased linearly at a rate of 60°C / min. A 3 / 8" diameter piece of separator is saturated with electrolyte and sandwiched between two electrode disks made from Al or Cu. An increase in resistance, measured as impedance, corresponds to the collapse of the pore structure due to melting or "shutdown" of the separator membrane. If the separator membrane sustains a high level of electrical resistance at high temperatures, this is an indication that the separator membrane can prevent shorting of the battery electrodes.

[0090] Gurley Gurley is defined as Japanese Industrial Standard (JIS) Gurley JIS P8117 and is a permeability test measured using an OHKEN permeability tester. JIS Gurley is the time (in seconds) required for 100cc of air to pass through 1 square inch of film at a constant water pressure of 4.8 inches.

[0091] mixed intrusion Mixed penetration is the force required to short through a separator when placed between cathode and anode materials. This test is used to indicate the tendency of a separator to short during battery assembly. Details of this method are described in US2010 / 209758.

[0092] Micro indentation Microindentation (also known as micropenetration) is the maximum force at which a fine micron conical indenter tip penetrates a non-conductive film sample and makes contact with a conductive substrate on a test stand as defined by a sudden drop in electrical resistance. The test method is described in U.S. Patent Application Publication No. 2014 / 0090480. It is expressed in units of mNf.

[0093] contact angle measurement The contact angles were measured using a Kruss Drop Shape Analyzer. The material was anhydrous propylene carbonate (PC). A 3 μL droplet of PC was carefully and gently dispensed onto the surface of the separator test sample. The contact angle was measured within 3 seconds of application of the PC droplet. The contact angle is reported in degrees.

[0094] According to at least selected embodiments, aspects or objectives, the present application or invention is directed to new or improved separator membranes, separators, batteries incorporating such separators, methods of making such membranes and / or separators, and / or methods of using such membranes and / or separators. According to at least one particular embodiment, the present invention relates to a microporous polyolefin, polyethylene (PE), copolymer, or polymeric material that has been treated with ionizing radiation. and / or polymer blends (e.g., copolymers or blends including PE and another polymer such as polypropylene (PP)) battery separators for secondary or rechargeable lithium batteries and / or methods of making ionizing radiation treated microporous battery separators.

[0095] The microporous membrane or battery separator of the present invention can provide a lower onset temperature of thermal shutdown, can have an extended thermal shutdown window where physical, dimensional and mechanical integrity is maintained at elevated temperatures, can improve battery safety performance in rechargeable lithium batteries, can provide a treated polyethylene separator membrane with the high temperature performance of polypropylene based tri-layer products (an example being a tri-layer membrane made of two polypropylene layers with a polyethylene layer between them), and can reduce heat shrinkage, providing both thermal stability and high temperature physical integrity, which can be important in maintaining separation between the cathode and anode of a battery system and avoiding thermal runaway events in rechargeable or secondary lithium batteries, and / or combinations thereof.

[0096] Ionizing radiation treatment of microporous polyethylene battery separators provides a method for lowering the onset temperature of thermal shutdown. Additionally, the microporous polyethylene battery separator membranes treated with ionizing radiation have an extended thermal shutdown window in which the physical, dimensional and mechanical integrity of the microporous separator membrane is maintained at higher temperatures. The extended high temperature dimensional integrity of the ionizing radiation treated separator membranes of the present invention improves the battery safety performance of rechargeable lithium ion batteries.

[0097] In addition, the increased high temperature dimensional integrity of the ionizing radiation treated separator membranes of the present invention approaches the high temperature performance of polypropylene based tri-layer products (one example being a tri-layer membrane consisting of two polypropylene layers with a polyethylene layer in between). In addition, the battery separator membranes of the present invention reduce heat shrinkage and provide both thermal stability and high temperature physical integrity, which can be important for maintaining separation of cathodes and anodes in battery systems and avoiding thermal runaway events in rechargeable or secondary lithium batteries.

[0098] Depending on at least selected embodiments, aspects, or objectives, the present application or invention may provide or is directed to new or improved or modified separator membranes, separators, batteries incorporating such separators, methods of making such membranes and / or separators, and / or methods of using such membranes and / or separators. According to at least one particular embodiment, the present invention is directed to polyolefin, polyethylene (PE), polypropylene (PP), copolymer and / or polymer blend (e.g., copolymer or blend including PE and another polymer such as, for example, polypropylene (PP)) membranes, microporous membranes, separator membranes, battery separators, and / or microporous battery separators for secondary batteries or rechargeable lithium batteries, and / or methods of making and / or using ionizing radiation treated membranes, microporous membranes, separator membranes, battery separators, and / or microporous battery separators.

[0099] The microporous membrane or battery separator of the present invention can provide a lower onset temperature of thermal shutdown, can have an extended thermal shutdown window where physical, dimensional and mechanical integrity is maintained at high temperatures, can have better oxidation resistance and can improve battery safety of rechargeable lithium batteries, can provide a treated polyethylene, polypropylene or polyolefin separator membrane, can provide a treated dry process product with performance that approaches or matches or exceeds that of wet process products, can provide a treated polyethylene, polypropylene or polyolefin separator membrane with higher temperature performance, can provide a treated polyethylene separator membrane with the high temperature performance of polypropylene based products, can provide a treated polyethylene separator membrane with the high temperature performance of polypropylene based products can provide a treated polyethylene separator membrane with high temperature performance for multi-layer or tri-layer products (by way of example only, a tri-layer membrane consisting of two polypropylene layers with a polyethylene or polypropylene layer in between, or a tri-layer membrane consisting of two polyethylene layers with a polypropylene or polyethylene layer in between), which may reduce heat shrinkage, resulting in both improved thermal stability and high temperature physical integrity, which may be important for maintaining separation of the cathode and anode in a battery system, improving high temperature, high energy, high charge rate, and / or high voltage capability, improving safety, and / or avoiding short circuit or thermal runaway events in rechargeable or secondary lithium batteries and / or combinations thereof.

[0100] The present invention may be embodied in other ways without departing from its spirit and essential characteristics, for example, crosslinking may be achieved via e-beam, heat, light, additives, chemicals, and the like. Accordingly, reference should be made to the appended claims, rather than the foregoing specification, as indicating the scope of the invention. Moreover, the invention disclosed herein may suitably be practiced in the absence of any element not specifically disclosed herein.

Claims

1. 1. A microporous battery separator membrane, comprising: a microporous polyolefin separator membrane having a thickness of less than 14 μm; the microporous separator membrane initiates a thermal shutdown at a temperature of 138° C. or less; the microporous separator membrane has a machine direction heat shrinkage of 7.5% or less at 120° C. for 1 hour; the microporous separator membrane has a transverse heat shrinkage of 1% or less at 120° C. for 1 hour; and / or A microporous polyolefin battery separator membrane, wherein said microporous separator membrane has been modified or altered using ionizing radiant energy.

2. 10. The separator membrane of claim 1, wherein the microporous separator membrane is modified and altered using low energy electron beam radiation.

3. 3. The separator membrane of claim 2, wherein the low energy electron beam radiation is at a dose of at least 50 kGy and at most 150 kGy.

4. The separator membrane of claim 2 , wherein the low energy electron beam radiation is applied using a single dose application step.

5. The separator membrane of claim 2 , wherein the microporous separator membrane is a single layer membrane, a multilayer membrane, a single-ply structure, or a multi-layer structure.

6. The separator membrane of claim 2 , wherein the microporous separator membrane comprises polyethylene.

7. The separator membrane of claim 1 , wherein the polyolefin is a semi-crystalline polymer.

8. 2. The separator membrane of claim 1, wherein the polyolefin is polyethylene or polypropylene.

9. 9. The separator membrane of claim 8, wherein the polyolefin is polyethylene, the polyethylene having a molecular weight of less than 800,000.

10. 9. The separator membrane of claim 8, wherein the polyolefin is polyethylene and the polyethylene microporous separator membrane is manufactured using a wet process.

11. The separator film has an electrical resistance of 1000 ohm cm ２ The separator membrane of claim 1, wherein the thermal shutdown window is expanded from 138° C. or less to 155° C. or more, or from 138° C. or less to 160° C. or more, or from 138° C. or less to 170° C. or more.

12. 13. A rechargeable lithium ion battery comprising the microporous polyolefin battery separator membrane of claim 1.

13. A method for producing a wetter polyethylene battery separator comprising providing a polyethylene battery separator and treating said separator with low energy electron beam radiation.

14. The low energy electron beam radiation treatment includes a dose in the range of 50 to 150 kGy. The method according to claim 13.

15. 1. A microporous battery separator membrane, comprising: a microporous polyolefin separator membrane having a thickness of less than 14 μm; The microporous separator membrane is Initiation of thermal shutdown occurs at temperatures below 138°C; A machine direction heat shrinkage of 7.5% or less at 120° C. for 1 hour; Thermal shrinkage in the transverse direction of less than 1% at 120℃ for 1 hour At least one of the following is included: The microporous separator membrane is a microporous polyolefin battery separator membrane that has been improved and / or modified by crosslinking.

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