KR20150036701A - High temperature melt integrity separator - Google Patents

Abstract

A heat resistant material based on an amorphous thermoplastic polymer that is resistant to but compatible with an electrolyte solution is disclosed. In one embodiment, the refractory material is used to form a battery cell and / or a separator for an electrolytic capacitor cell.

Description

[0001] HIGH TEMPERATURE MELT INTEGRITY SEPARATOR [0002]

The battery cell and the electrolytic capacitor cell typically include an anode and a cathode (cathode and anode) and an electrolyte solution. The electrodes are separated by a thin porous film known as a separator. The separator plays a key role in the battery / capacitor. One function of the separator is to prevent electrical shorts by maintaining the two electrodes physically separated from each other, and thus the separator must be electrically insulated. At the same time, the separator must quickly transport the charge carriers needed to complete the circuit during cell charging and discharging. Thus, a battery separator must have the ability to conduct ions either as a proprietary ion conductor (such as a solid electrolyte) or by soaking with an ion-conducting liquid electrolyte.

The high temperature melt integrity (HTMI) of the battery separator is a key characteristic to ensure the safety of the entire battery pack as well as the individual cells. High temperature melt integrity can provide safety when it results in internal heat build up due to overcharging or internal shorting, or increased internal cell temperature, and the separator maintains integrity (shape and mechanical integrity) It is possible to prevent contact with each other.

Typical separators for lithium-ion batteries are based on polymers, more specifically polyethylene (PE) and polypropylene (PP), which are produced through melt processing techniques. These types of separators typically have poor melt integrity at high temperatures (< 160 [deg.] C) and are poorly wettable by the electrolyte solution. Thus, there is a need for an improved HTMI and an alternative separator with electrolyte wettability that can be produced through a melt or solution process.

Porosity of lithium-ion batteries, polymeric separator films is typically induced by stretching (uniaxial) stretching of the extruded film, which process is known as the "dry process ", and the complex interactions between the extrusion, (See, for example, U.S. Patent Nos. 3,558,764 and 5,385,777). The dry process typically results in an open pore structure and a relatively uniform pore size. However, the drying process inherent in the stretching process causes non-spherical pores and residual stress in the material. The residual stress typically results in film strain (shrinkage), especially at elevated temperatures. In order to grow the porous structure, crystallization / crystallization is required during the stretching process, so that the production of the porous film by the dry process is limited to the semi-crystalline polymer. Through this process, a moderately high porosity (30-50%) can be obtained, but the actual porosity (measured, for example, by air permeability) is generally considerably lower since not all pores are interconnected.

Porosity can also be induced by premixing the polymer with a low molecular weight extractable species, which forms a specific structure upon cooling from the melt and leaves a porous structure after removal of the low molecular weight species (see, for example, U.S. Patent No. 7,618,743 And Japanese Patent Nos. 1988273651, 1996064194, and 1997259858). This process is known as a "wet process" and typically uses a polymer / extractable combination that is miscible during the extrusion process, but phase separates upon cooling. Extractable species are typically low molecular weight species such as hydrocarbon liquids, such as paraffin oil. Removal of low molecular weight species can be achieved by evaporation or extraction. Extraction is typically accomplished using an organic volatile solvent such as methylene chloride. Typically, additional stretch (uniaxial or biaxial) steps are used to create the desired pore structure. The wet process typically results in highly curved interconnected porous structures. The production of porous films by wet processes is typically limited to polymers with relatively high melt strength (e.g. ultra-high molecular weight polyethylene). Similar to the dry process, the actual porosity (measured, for example, by air permeability) is substantially lower than the total porosity because not all pores are interconnected to each other.

The high porosity of the separator film is typically beneficial to the charge and discharge characteristics of the battery, as the cell volume resistance decreases as the separator porosity increases. The separator pore size needs to be smaller than the particle size of the anode and cathode active materials (typically 2-3 micrometers). Also, the pore size distribution should be narrow, and the pores should be uniformly distributed. Preferably, all the pores can be connected from the front side to the back side of the film, i.e., the actual porosity should be equal to the total porosity. This means that the electrolytic solution is accessible to all pores and contributes to ion transport through the separator. In the case of Li-ion batteries, high tortuosity and interconnected pore structures are beneficial for long-life batteries because they inhibit the growth of lithium crystals on the graphite anode during rapid charging or cold charging. On the other hand, an open (low curvature) uniform pore size structure is beneficial for applications requiring rapid charging and discharging, such as high power density batteries.

The separator films of non-aqueous batteries are mostly based on polymers, more specifically based on polyethylene (PE) and polypropylene (PP). Both PE and PP are used because of the known solvent resistance to the electrolyte solution, which enables long-term performance of the separator in the battery cell. A distinct disadvantage of this type of separator is poor low temperature integrity integrity (HTMI) and poor interaction (i.e., wettability and electrolyte retention) with the electrolyte solution.

Research is underway to develop a separator film with improved HTMI performance (> 180 ° C). Two technical approaches are typically used to achieve improved HTMI performance (> 180 DEG C). The first is to use a ceramic coating or filler to strengthen the porous polymer matrix. Examples include:

- Alumina (Al ₂ O ₃ ) manufactured by Mitsubishi Chemical Company and a hybrid separator based on PVdF binder [Technologies and Market Forecast of Separators for Rechargeable Lithium Ion Batteries, September 2010, Solar & Energy Co., Ltd. Reference].

- a hybrid separator composed of ceramic particles bonded on a nonwoven polyester developed by Degussa [S. Zhang, A review on separators of liquid electrolyte Li-ion batteries, J Power Sources (2007) 164: 351-364].

- LG Chemical developed a so-called "SRS" (safety-enhanced separator) using a polyolefin separator coated with a ceramic layer. In this case, the ceramic layer improves the thermal stability and mechanical strength of the separator [X. Huang, Separator technologies for lithium-ion batteries, J Solid State Electrochem (2011) 15: 649-662, United States Patent Application 20100255382].

- Sony Corp. [United States Patent Application 20090092900] and Panasonic [United States Patent Application 20100151325, 20080070107] developed a polymer type separator coated with a heat resistant inorganic layer.

- Samsung [United States Patent Application 20090155677] has developed a polymeric separator filled with inorganic particles.

- GM [US Patent Application 20110200863] developed an oxygen plasma process for coating a porous polymer membrane with an electrically resistive ceramic material.

- Teijin [International Patent Application 2008062727] developed a microporous polyethylene film having a heat-resistant porous layer composed of fine inorganic particles.

- Asahi [International Patent Application 2008093575] has developed a multilayer porous film comprising a polyolefin resin porous film, an inorganic filler and a resin binder.

Application of a ceramic layer to a polymeric membrane typically degrades mechanical properties (e.g., tensile strength and flexibility), which compromises the integrity of the separator during cell preparation as well as the safety during actual application of the cell. In addition, applying a ceramic layer to the polymeric separator is undesirable because it involves a secondary processing step. Such secondary processing requires very strict control because events such as coating / matrix separation and / or particle removal need to be prevented, which results in significant additional costs. In addition, the inorganic coating applied to allow ion transport through the separator during cell charging and discharging needs to be porous.

Another approach to improve the HTMI of the separator is to replace the polyethylene or polypropylene polymer matrix with a heat resistant polymer. Examples of such highly heat resistant polymers include poly (4-methylpentene) (PMP) [European Patent 2308924, US Patent Application 20060073389] and crosslinked polymers [US Patent 4522902]. Disadvantages of these approaches are poor wettability and difficult process by the electrolyte, respectively. US20130125358A1, CN102251307A, US20110143217A1, and US20110143207A1 disclose the use of wholly aromatic polyimides for battery separator applications. However, it is difficult to process a wholly aromatic polyimide into a porous film because the wholly aromatic polyimide is thermosetting, and is therefore typically incapable of melt processing. Application of melt and solution processable thermoplastic polyetherimide (PEI) for battery separator applications in a variety of structural forms is disclosed, for example, in CA2468218A1, DE102010024479A1, US7814672B2, US7214444B2, US7087343B2 and US20110171514A1, US20110165459A1, US20120308872A1, US20120309860A1, US20120156569, US8470898B2, JP2005209570A, JP2009231281A, JP2009231281A. However, polyetherimides typically do not have the solvent resistance necessary for application in a battery environment, which results in significant dissolution and / or swelling of the separator, which separates the electrodes physically while allowing the ion transport through the pores (Partial) loss of ability. Polyetherimides containing structural units derived from polyetherimides with improved solvent resistance, for example para-phenylenediamine, are known. However, these types of solvent-soluble polyetherimides are typically considered to be impractical for solution processing. As far as we know, the solvent-soluble polyetherimide comprising structural units derived from para-phenylenediamine has never been applied as a battery separator.

Thus, there continues to be a need for a polymeric separator film that is essentially compatible with, and resistant to, non-aqueous electrolyte solutions and has a melt integrity of greater than 180 DEG C, wherein the separator is based on a thermoplastic polymer, Can be prepared by the same single-step process.

In the use of lithium-ion batteries, the separator must meet a series of characteristics such as ionic conductivity and modulus, which are in particular induced by the microporous form. Conventional PP and PE separators are produced by so-called dry or wet processes, all of which are dependent on stretching, crystallization and annealing of the polymer to produce the desired pore structure. Since the polyetherimide is typically an amorphous resin, these two conventional approaches are not suitable for the production of polyetherimide-based separators. Thus, there is a need for a process for preparing a separator suitable for para-phenylenediamine-based polyetherimides, in which case this process enables the production of a porous structure that meets the requirements of a battery separator.

Disclosed are materials that provide high temperature melt integrity and improved electrolyte wettability for environments such as batteries or electrolytic capacitor cells. As an example, a separator for a battery cell and / or a capacitor cell can be formed from the disclosed material. As a further example, other structures and systems may implement the disclosed materials.

In one embodiment, the separator film may be formed from a thermoplastic such as an amorphous thermoplastic (e.g., polyetherimide (PEI)). For example, a separator film formed from a polyetherimide (PEI) based on para-phenylenediamine (ULTEM (TM) CRS 5000 series of SABIC) has a high compatibility with electrolyte, a high solvent resistance and a high melt integrity temperature Equal performance characteristics. &Lt; RTI ID = 0.0 &gt; The polyetherimide (PEI) based on para-phenylenediamine meets the critical requirement for resistance to electrolyte solutions even at elevated temperatures of 55 &lt; 0 &gt; C. In addition, the polyetherimide exhibits an extremely low contact angle (e.g., &lt; 30 DEG) for the electrolyte solution, which is advantageous for separator wettability and electrolyte retention, thereby reducing electrolyte charge time during cell preparation. Surprisingly, separators made from polyetherimides based on para-phenylenediamine significantly improve on-cell performance, such as battery cycle life. Separators from PEI based on para-phenylenediamine have very high melt integrity (above 180 ° C.) and high elasticity (stiffness) over the entire range of cell operation (ie, physical properties such as glass transition or crystal melting Polymer transition does not occur in the cell operating temperature window). The proposed material is capable of both melting and solution processing into a porous film with a specific ionic conductivity equal to or superior to that of a typical commercial polyolefin-based separator.

In one aspect, the system can include an anode, a cathode, and a separator disposed between the anode and the cathode, wherein the separator is formed from a thermoplastic polymer having a glass transition temperature of 180 캜 or higher.

In one aspect, the system can include an anode, a cathode, and a separator disposed between the anode and the cathode, wherein the separator is formed from an amorphous thermoplastic polymer, the electrolyte is disposed adjacent to the separator (e.g., as wetting, soaking, dipping, etc.), wherein the amorphous thermoplastic polymer is one that has an electrolyte (1mol / L LiPF ₆ of less than 30 °: 1: 1 ratio of DMC: EMC: EC) has a contact angle.

In one embodiment, the method may include the steps of forming a separator from a thermoplastic polymer using a melting or solution process, disposing a separator between the anode and the cathode, and disposing the electrolyte adjacent the separator.

In one embodiment, the separator may be made from a resin, and thus this material is transformed into a porous film. By way of example, the separator may be formed by stretching the extruded film or by washing the solute in an extruded film. Other methods for forming the separator can also be used.

In one embodiment, a method for making a solvent-resistant polymeric membrane may comprise providing an injectable polymeric solution comprising a chemical resistant polymer in a solvent and forming a membrane from the polymeric solution.

A method for making a porous film may include providing an injectable polymer solution comprising a chemical resistant polymer in a solvent and forming a porous film from the polymer solution.

In one embodiment, a phase separation process based on SABIC's ULTEM (TM) CRS 5000 resin can be used to fabricate a lithium ion battery separator. Phase separation can be induced by exposing the polymer solution to a non-solvent in a liquid state (liquid-induced phase separation, LIPS) or a vapor state (vapor-induced phase separation, VIPS). Key factors including the composition of the dope (polymer) solution, the solidification bath and the temperature have been studied to achieve the desired shape and properties. Both LIPS and VIPS have been found to be suitable for producing ULTEM ™ CRS 5000 porous separator films capable of tuning pore structures, which are well suited for battery separator applications. A separator was prepared which meets the typical separator requirements for porosity, pore size, thickness, conductivity and Young's modulus. This process is versatile with respect to the porosity, pore size and thickness obtained, and therefore is versatile in the final performance of the separator in an actual electrochemical cell environment. The separator significantly improves the cycle life of the battery as compared to a commercially available polyolefin-based separator. As far as we know, this is the first example of a ULTEM ™ CRS 5000 separator manufactured through the LIPS or VIPS process, and the first example of a separator formed successfully applied to a lithium-ion battery.

Phase separation of the polymer in solution is a well known process for preparing microporous membranes, for example, for filtration applications, typically in the form of hollow fibers. In one embodiment, the phase separation can be induced by a variety of means including temperature, chemical reaction, liquid non-solvent and vapor non-solvent. For example, U.S. Patent 5,181,940 discloses the use of this phase separation approach for producing asymmetric hollow fiber membranes for gas separation applications. Typically, the use of this phase separation approach results in a thin and dense shell layer on the outer surface of the membrane. Typically, such dense shell layers are required for gas separation applications, for example, but such dense shell layers prevent ion transport through the membrane, making the membrane unsuitable for battery separator applications, and thus are not very desirable for battery separator applications. (PEEK), polyether imide (PEI), and polyphenylene sulfide (PEEK), for example, in German Patent 3,321,860, European Patent 182506, US Patents 4,755,540, 4,957,817, 4,992,485, 5,227,101, 6,017,455 and 5,997,741 Various approaches for producing a porous film from a solvent-resistant polymer such as PPS have been disclosed. These methods typically use acidic solvents and / or high temperature processes. In addition, U.S. Patent Nos. 3,925,211 and 4,071,590 disclose the preparation of membranes through the formation of soluble film pre-polymers that are converted to final porous membranes through chemical reactions. It may be more beneficial to raise the temperature or to prepare the porous film directly from the polymer solution without the need to introduce an acidic solvent or chemical reaction. Liquid-Induced Phase Separation (LIPS) processes for making flat sheet membranes based on solvent-soluble PEI, PI, PEEK and PPS have already been disclosed (see U.S. Patent Application Nos. 2007/0056901 and 2007/0060688; and U.S. Patent No. 7,439,291) In which case the polymer is at least partially crystalline. Because these classes of polymers are generally known to be solvent soluble, co-solvent systems have been reported for dissolving the solvent polymer at elevated temperatures and keeping it in solution at room temperature. The disclosed solvent systems are based on p-chloro-2-methyl-phenol in combination with (para-, meta-, ortho- and chloro-) cresols. However, the claimed process, and more specifically the disclosed solvent / anti-solvent combination, enables the production of porous structures, but typically does not provide a membrane suitable for battery separator applications. We can control the shape (eg, thickness, porosity, mechanical properties and porous structure) of the separator by using a LIPS or VIPS process based on solvent-soluble amorphous polyetherimide grades and an optimized solvent system, , Electrolyte wettability and battery cell performance. &Lt; Desc / Clms Page number 2 &gt; In addition, we have applied a solvent-resistant polyetherimide to a solvent with reduced toxicity (lower health rankings on the American Fire Protection Association (NFPA) Fire Diamond under the US Centers for Disease Control and Prevention - http://www.cdc.gov) I found a way to dissolve it.

Additional advantages will be set forth in part in the description that follows, or may be learned by practice. The advantages will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention.

The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments and, together with the description, serve to explain the principles of the method and system.
1 is a schematic diagram of an exemplary battery cell.
Figure 2 shows a representative form (cross-section) of a solvent coated ULTEMTM CRS 5001 separator.
3 is a graph showing the discharge capacity retention of a plurality of separators.
Fig. 4 shows a form obtained by preparing a porous film according to Example 1. Fig.
Fig. 5 shows a form obtained by preparing a porous film according to Example 2. Fig.
Fig. 6 shows a form obtained by preparing a porous film according to Example 3. Fig.
Fig. 7 shows a form obtained by producing a porous film according to Example 4. Fig.
Fig. 8 shows a form obtained by preparing a porous film according to Example 5. Fig.
Fig. 9 shows a form obtained by producing a porous film according to Example 6. Fig.
Fig. 10 shows a form obtained by producing a porous film according to Example 7. Fig.
Fig. 11 shows a form obtained by preparing a porous film according to Example 8. Fig.
Fig. 12 shows a form obtained by producing a porous film according to Example 9. Fig.
Fig. 13 shows a form obtained by producing a porous film according to Example 10. Fig.
Fig. 14 shows a form obtained by producing a porous film according to Example 11. Fig.
Fig. 15 shows a form obtained by producing a porous film according to Example 12. Fig.
Fig. 16 shows a form obtained by preparing a porous film according to Example 13. Fig.
Fig. 17 shows a form obtained by preparing a porous film according to Example 14. Fig.
Fig. 18 shows a form obtained by producing a porous film according to Example 16. Fig.
Fig. 19 shows a form obtained by producing a porous film according to Example 17. Fig.
Fig. 20 shows a form obtained by preparing a porous film according to Example 18. Fig.
Fig. 21 shows a form obtained by producing a porous film according to Example 19. Fig.
Fig. 22 shows a form obtained by producing a porous film according to Example 20. Fig.
Fig. 23 shows a form obtained by producing a porous film according to Example 21. Fig.
24 shows a form obtained by producing a porous film according to Example 22. Fig.
Fig. 25 shows a form obtained by producing a porous film according to Example 23. Fig.
Fig. 26 shows a form obtained by producing a porous film according to Example 4. Fig.
Fig. 27 shows a form obtained by producing a porous film according to Example 5. Fig.
Fig. 28 shows a form obtained by producing a porous film according to Example 7. Fig.
Fig. 29 shows a form obtained by producing a porous film according to Example 11. Fig.
30 shows a form obtained by preparing a porous film according to Example 16. Fig.
Fig. 31 shows a form obtained by producing a porous film according to Example 17. Fig.
Fig. 32 shows a form obtained by producing a porous film according to Example 18. Fig.
Fig. 33 shows a form obtained by producing a porous film according to Example 19. Fig.
Fig. 34 shows a form obtained by producing a porous film according to Example 20. Fig.
Fig. 35 shows a form obtained by producing a porous film according to Example 21. Fig.
Fig. 36 shows a form obtained by preparing a porous film according to Example 22. Fig.
Fig. 37 shows a form obtained by preparing a porous film according to Example 23. Fig.
38 is a graph showing the apparent porosity of the selected sample.
39 is a graph showing the conductivity of the selected sample.
40 is a graph showing the stress at 2% offset of the selected sample.
41 is a graph showing the temperature fusion integrity of the selected sample.
42 is a graph showing the discharge capacity retention of Example 20 compared with a commercial separator (Celgard ^® 2320).
Fig. 43 shows a form obtained by producing a porous film according to Example 24. Fig.
44 shows a form obtained by producing a porous film according to Example 25. Fig.
Fig. 45 shows a form obtained by preparing a porous film according to Example 26. Fig.
Figure 46 is a graph showing the melting temperatures of ULTEMTM CRS 5001K and ULTEMTM CRS 5011K in NMP as a function of concentration.
47 is a graph showing the "rectified-state" phase separation temperature.
48A shows an example form obtained by casting according to Example 30. Fig.
48B shows an enlarged view of an example form obtained by casting according to the embodiment 30. Fig.
49A shows an example form obtained by casting according to Example 31. Fig.
49B shows an enlarged view of an example form obtained by casting according to Example 31. Fig.
50A shows an example form obtained by casting according to Example 32. Fig.
Fig. 50B shows an enlarged view of an example form obtained by casting according to Example 32. Fig.
51A shows an example form obtained by casting according to Example 33. Fig.
51B is an enlarged view of an example form obtained by casting according to Example 33. Fig.
52A shows the lower surface of an example form obtained by casting according to Example 34. Fig.
52B shows a cross section of an exemplary embodiment obtained by casting according to Example 34. Fig.
53A shows the lower surface of an example form obtained by casting according to Example 35. Fig.
53B shows a cross-section of an exemplary embodiment obtained by casting according to Example 35. Fig.
54 shows a cross section of an exemplary embodiment obtained by casting according to Example 36. Fig.
55 shows a cross section of an exemplary embodiment obtained by casting according to Example 37. Fig.
56 shows an example form obtained according to Example 38. Fig.
57 shows an example form obtained according to Example 39. Fig.
58 shows an example form obtained according to Example 40. Fig.
59 shows an example form obtained according to Example 41. Fig.
60 shows an example form obtained according to Example 42. Fig.
61 shows an example form obtained according to Example 43. Fig.
62 shows an example form obtained according to Example 44. Fig.
63 shows an example form obtained according to Example 45. Fig.
Fig. 64 shows an example form obtained according to Example 46. Fig.

Before disclosing and describing the present methods and systems, it should be understood that the present methods and systems are not limited to any particular method of synthesis, specific components, or specific compositions. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

The singular forms "a" and "its" used in the specification and the appended claims include the plural reference unless the context clearly dictates otherwise. Ranges may be indicated herein by "about" one particular value, and / or by "about" other particular value. When such a range is indicated, other embodiments include at one particular value and / or to the remaining specific value. Similarly, it will be appreciated that when values are expressed in approximate terms using the "about" preceding, certain values form different embodiments. Furthermore, each endpoint of the range is significant both in relation to the remaining endpoints and independently of the other endpoint.

"Optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event or circumstance occurs and instances in which it does not.

The word "comprises" and variations thereof, such as "comprising" and "including," means "including, but not limited to," It is not intended to exclude components, integers, or steps. "Exemplary" means "yes ", and is not intended to convey any indication of a preferred or ideal embodiment. The "same" is used for descriptive purposes rather than in a limiting sense.

Disclosed are components that can be used in the performance of the disclosed methods and systems. While these and other components are disclosed herein and the specific recitation of each of the various individual and collective combinations and permutations of these components is not explicitly disclosed when a combination, subset, interaction, group, etc. of these components is disclosed, Each of which is specifically contemplated and described herein with respect to all methods and systems. This applies to all aspects of the present application including, but not limited to, the steps of the disclosed method. Thus, if there are various additional steps that can be performed, it is understood that these additional steps may each be performed with any particular embodiment or combination of embodiments of the disclosed method.

The method and system may be more readily understood with reference to the following detailed description of the preferred embodiments, the embodiments contained therein, and the drawings and their previous and subsequent description.

Although some attempts have been made to ensure accuracy with respect to numbers (eg, quantity, temperature, etc.), some errors and deviations should be considered. Unless otherwise indicated, parts are parts by weight, temperatures are in ° C or ambient temperature, and pressures are atmospheric or atmospheric pressure approximations.

Figure 1 shows an exemplary non-aqueous electrolyte battery. It will be understood by those skilled in the art that the electrolytic capacitor cell may have a configuration similar to that illustrated and described with reference to FIG. In one aspect, the battery includes an anode 100 (cathode), a cathode 102 (anode), and a separator 104 disposed between the anode 100 and the cathode 102. By way of example, one or more of the anode 100, the cathode 102, and the separator 104 are housed in a battery container or casing 106. As a further example, a non-aqueous electrolyte 108 can be disposed in the casing 106 (e.g., adjacent one or more of the anode 100, the cathode 102, and the separator 104) Soaking, separator 104 dipping, etc.).

In one embodiment, the anode 100 may comprise an integrated cathode active material and may further comprise an electrically conductive material such as carbon and / or a binder to aid in the sheetification or pelletization of the cathode active material. The anode 100 can be used in contact with an electron conductive substrate such as a metal as a current collector. By way of example, the binder may be formed from polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), ethylene-propylene-diene copolymer, styrene-butadiene rubber and the like. As another example, the current collector may be formed from foil, thin sheet, mesh or gauze of metal such as aluminum, stainless steel and titanium. As a further example, the positive electrode active material and / or the conductive material may be pelletized or sheeted together with the above-mentioned binders by kneading / rolling. In addition, these materials may be dissolved and suspended in a solvent such as toluene and N-methylpyrrolidone (NMP) to form a slurry, and then spread and dried on the above-mentioned current collector to obtain a sheet. Other materials and forming processes may also be used.

In one embodiment, the anode 100 may include a lithium composite oxide containing at least one of iron, cobalt, manganese, and nickel as a cathode active material capable of intercalating / deintercalating lithium ions. A lithium-containing iron complex oxide, a lithium-containing cobalt composite oxide, a lithium-containing nickel-cobalt composite oxide, a lithium-containing nickel composite oxide and a lithium-manganese composite oxide, Can be used as an active substance. Other materials and forming processes may also be used.

In one embodiment, the cathode 102 may comprise an integrated negative active material. For example, the cathode 102 may be formed by pelletizing, tableting, or sheeting the anode active material together with a conductive material, a binder, and the like. In one embodiment, the conductive material may be formed from an electron conductive material such as carbon or metal. By way of example, the binder may be formed from polytetrafluoroethylene, polyvinylidene fluoride, styrene-butadiene rubber, carboxymethylcellulose, and the like. As another example, the current collector may be formed from a foil such as copper, stainless steel, nickel, a thin plate, a mesh or a gauze. As a further example, the negative electrode active material and / or the conductive material may be pelletized or sheeted together with the above-mentioned binders by kneading / rolling. In addition, these materials can be dissolved and suspended in a solvent such as water and N-methylpyrrolidone to form a slurry, and then spread and dried on the above-mentioned current collector to obtain a sheet. Other materials and forming processes may also be used.

In one embodiment, the cathode 102 may contain lithium (or lithium ions) or may occlude / release lithium (or lithium ions) similarly to the above-mentioned anode. As an example, the cathode 102 may contain lithium ion-containing or an integrated negative active material capable of intercalating / deintercalating lithium ions at a potential that is more negative than the potential of the anode 100 in combination with the cathode 102 . Examples of the negative electrode active material having such characteristics include lithium metal; Carbonaceous materials (carbon-based materials) such as artificial graphite, natural graphite, non-graphitizable carbon and graphitizable carbon; Graphene; Carbon nanotubes; Lithium titanate; Iron; Cobalt oxide; Lithium-aluminum alloy; silicon; And tin oxide. Other materials and forming processes may also be used.

In one embodiment, the separator 104 may be formed from a polyetherimide (PEI) based on para-phenylenediamine (e.g., ULTEM (TM) CRS 5000 series). As an example, a battery separator film (e.g., separator 104) formed from polyetherimide (PEI) based on para-phenylenediamine has high compatibility with electrolyte, high solvent resistance, and high melt integrity Temperature, and so on. The polyetherimide (PEI) based on para-phenylenediamine can meet critical requirements that must be resistant to battery electrolyte solutions even at elevated temperatures of 55 &lt; 0 &gt; C. In addition, these materials exhibit an extremely low contact angle for the electrolyte solution over the entire composition range typically used in the electrolyte, which is advantageous for separator wettability and electrolyte retention, thereby reducing the electrolyte charge time during cell preparation. Separators from PEI based on para-phenylenediamine have very high melt integrity (above 180 DEG C) and high elasticity (stiffness) over the entire range of cell operation. Separators from PEI based on para-phenylenediamine significantly improve battery cycle life. The proposed thermoplastic material is capable of both melting and solution processing into porous films with specific ionic conductivities equal to or better than typical commercial polyolefin-based separators. Other materials and forming processes may also be used. In one embodiment, the electrolyte comprises 0 wt% to 50 wt% ethyl carbonate of the total solvent composition; 0 wt% to 80 wt% dimethyl carbonate of the total solvent composition; And 0 wt% to 80 wt% ethyl methyl carbonate in the total solvent composition.

In one embodiment, the separator 104 dissolves the solvent-soluble polyetherimide in a phenolic solvent at elevated temperature (120 占 폚), then casts at a reduced temperature (20 to 50 占 폚) &Lt; / RTI &gt; For example, membranes such as battery cells and / or capacitor cells, electrolytic energy storage devices, dialysis membranes, water filtration membranes, desalination membranes, gas separation membranes, and the like can be fabricated using the materials and processes disclosed herein.

In one embodiment, the separator 104 is heated at an elevated temperature (140 to 202 ° C, see FIG. 1) in a closed system (i.e., there is no direct contact between the solution and the air atmosphere) By dissolving the solvent-soluble polyetherimide in NMP and then casting at reduced temperature (30 to 140 DEG C) and solidifying in a bath of water or other material. For example, membranes such as battery cells and / or capacitor cells, electrolytic energy storage devices, dialysis membranes, water filtration membranes, desalination membranes, gas separation membranes, and the like can be fabricated using the materials and processes disclosed herein.

In one embodiment, the polyetherimide may comprise a polyetherimide homopolymer (e.g., polyetherimide sulfone) and a polyetherimide copolymer. The polyetherimide may be selected from i) a polyetherimide homopolymer, such as a polyetherimide, ii) a polyetherimide copolymer, and iii) a combination thereof. Polyetherimides are known polymers and are sold by SABIC Innovative Plastics under the ULTEM® *, EXTEM® *, and Siltem * brands (trade names of SABIC Innovative Plastics IP B.V.).

In one embodiment, the polyetherimide may have formula (1): &lt; EMI ID =

Where a is greater than 1, for example from 10 to 1,000, or, more specifically, from 10 to 500.

The group V in formula (1) is a saga linker containing an ether group ("polyetherimide" used herein) or a combination of an ether group and an arylene sulfone group ("polyetherimide sulfone"). Such linkers include, but are not limited to, (a) substituted or unsubstituted, saturated, unsaturated, or aromatic groups having 5 to 50 carbon atoms, optionally substituted with a combination of ether groups, arylene sulfone groups, or ether groups and arylene sulfone groups Or aromatic monocyclic and polycyclic groups; And (b) a substituted or unsubstituted, linear or branched, saturated or unsaturated alkyl group having from 1 to 30 carbon atoms, optionally substituted with a combination of ether groups or ether groups, arylene sulfone groups and arylene sulfone groups, group; Or combinations comprising at least one of the foregoing. Suitable further substituents include, but are not limited to, ether, amide, ester, and combinations comprising at least one of the foregoing.

The R group in formula (1) includes, but is not limited to, a substituted or unsubstituted bivalent organic group such as (a) an aromatic hydrocarbon group having 6 to 20 carbon atoms and halogenated derivatives thereof; (b) a straight or branched alkylene group having from 2 to 20 carbon atoms; (c) a cycloalkylene group having 3 to 20 carbon atoms, or (d) a divalent group of formula (2)

Wherein Q ¹ is selected from the group consisting of -O-, -S-, -C (O), -SO ₂ -, -SO-, -CyH ₂ y- (y is an integer from 1 to 5) And halogenated derivatives thereof including haloalkyl groups.

In one embodiment, linker V includes, but is not limited to, a saga aromatic group of formula (3):

Wherein W is a bivalent moiety including a group of -O-, -SO ₂ -, or a group of the formula -OZO-, and the bivalent bond of the -O- or -OZO- group is 3,3 ', 3,4', 4,3 ', Or 4,4' position, where Z includes, but is not limited to, a divalent group of formula (4):

Wherein Q is, restriction is not -O-, -S-, -C (O) , -SO 2 -, -SO-, -CyH 2 y- (y is an integer of 1 to 5), and perfluoro And halogenated derivatives thereof including alkylene groups.

In one embodiment, the polyetherimide may comprise more than one structural unit of formula (5), and may specifically comprise from 10 to 1,000, or, more specifically, from 10 to 500:

Wherein T is a group of the formula -O- or a formula -OZO-, the bivalent bond of the -O- or -OZO- group is in the 3,3 ', 3,4', 4,3 'or 4,4' Wherein Z is a bivalent linkage of formula (3) as defined above and R is a divalent linkage of formula (2) as defined above.

In another embodiment, the polyetherimide sulfone is a polyetherimide comprising an ether group and a sulfone group, wherein at least 50 mole percent of the linker V and R groups in formula (1) comprises a bivalent arylene sulfone group. For example, all Linker V except for the R group may contain an arylene sulfone group, or all R groups except for the linker V may contain an arylene sulfone group, or an arylene sulfone may contain part of the linker V and the R group , With the proviso that the total mole fraction of V and R groups containing arylsulfone groups is at least 50 mole%.

More specifically, the polyether imide sulfone may comprise more than 1, specifically 10 to 1,000, or more specifically 10 to 500 structural units of formula (6)

Y is a group of -O-, -SO ₂ -, or -OZO-, and the bivalent bond of -O-, SO ₂ -, or -OZO- group is 3,3 ', 3,4' 3 'or 4,4' position, wherein Z is a divalent linking group of formula (3) as defined above, R is a divalent linking group of formula (2) as defined above, More than 50 mole% of the sum of the mole Y + mole R contains -SO ₂ - groups.

It is to be understood that the polyetherimide and polyetherimide sulfone may optionally include a linker V which does not contain an ether or ether and a sulfone group, for example a linker of formula (7)

The imide unit containing such linker is generally present in an amount ranging from 0 to 10 mole%, specifically from 0 to 5 mole%, of the total number of units. In one embodiment, no additional linker V is present in the polyetherimide and polyetherimide sulfone.

In another embodiment, the polyetherimide comprises 10 to 500 structural units of formula (5) and the polyetherimide sulfone contains 10 to 500 structural units of formula (6).

The polyetherimide and polyetherimide sulfone can be prepared by any suitable process. In one embodiment, the polyetherimide and polyetherimide copolymers comprise a polycondensation polymerization process and a halo-displacement polymerization process.

Polymer condensation polymerization may include a method for the preparation of polyetherimides having structure (1) wherein the nitro-displacement process (X in formula (8) is nitro). In one example of the nitro-displacement process, N-methylphthalimide is nitrated with 99% nitric acid to form N-methyl-4-nitropthalimide (4-NPI) A mixture of imide (3-NPI) is obtained. After purification, a mixture containing approximately 95 parts of 4-NPI and 5 parts of 3-NPI is reacted in the presence of a phase transfer catalyst in di-sodium salt of bisphenol-A (BPA) and toluene. This reaction gives BPA-bisimide and NaNO ₂ , which is known as the nitro-displacement stage. After purification, BPA-bisimide is reacted with phthalic anhydride in the imide exchange reaction to obtain BPA-dianhydride (BPADA), which in turn is converted to meta-phenylenediamine (MPD) in ortho-dichlorobenzene in the imidization- &Lt; / RTI &gt; to yield a polyetherimide product.

Other diamines are also possible. Examples of suitable diamines include m-phenylenediamine; p-phenylenediamine; 2,4-diaminotoluene; 2,6-diaminotoluene; m-xylylenediamine; p-xylylenediamine; Benzidine; 3,3'-dimethylbenzidine; 3,3'-dimethoxybenzidine; 1,5-diaminonaphthalene; Bis (4-aminophenyl) methane; Bis (4-aminophenyl) propane; Bis (4-aminophenyl) sulfide; Bis (4-aminophenyl) sulfone; Bis (4-aminophenyl) ether; 4,4'-diaminodiphenyl propane; 4,4'-diaminodiphenylmethane (4,4'-methylenedianiline); 4,4'-diaminodiphenylsulfide; 4,4'-diaminodiphenylsulfone; 4,4'-diaminodiphenyl ether (4,4'-oxydianiline); 1,5-diaminonaphthalene; 3,3'-dimethylbenzidine; 3-methylheptamethylenediamine; 4,4'-dimethylheptamethylenediamine, 2,2 ', 3,3'-tetrahydro-3,3,3', 3'-tetramethyl-1,1'-spiro [ 6'-diamine; 3,3 ', 4,4'-tetrahydro-4,4,4', 4'-tetramethyl-2,2'-spiro [2H-1-benzo-pyran] -7,7'-diamine; 1,1'-bis [1-amino-2-methyl-4-phenyl] cyclohexane, and isomers thereof, as well as mixtures and blends comprising at least one of the foregoing. In one embodiment, the diamine is specifically a mixture comprising an aromatic diamine, especially m- and p-phenylenediamine, and at least one of the foregoing.

Suitable dianhydrides that may be used with diamines include, but are not limited to, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl ether dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) benzophenone dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfone dianhydride; 2,2-bis [4- (2,3-dicarboxyphenoxy) phenyl] propane dianhydride; 4,4'-bis (2,3-dicarboxyphenoxy) diphenyl ether dianhydride; 4,4'-bis (2,3-dicarboxyphenoxy) diphenyl sulfide dianhydride; 4,4'-bis (2,3-dicarboxyphenoxy) benzophenone dianhydride; 4,4'-bis (2,3-dicarboxyphenoxy) diphenyl sulfone dianhydride; 4- (2,3-dicarboxyphenoxy) -4 '- (3,4-dicarboxyphenoxy) diphenyl-2,2-propane dianhydride; 4- (2,3-dicarboxyphenoxy) -4 '- (3,4-dicarboxyphenoxy) diphenyl ether dianhydride; 4- (2,3-dicarboxyphenoxy) -4 '- (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride; 4- (2,3-dicarboxyphenoxy) -4 '- (3,4-dicarboxyphenoxy) benzophenone dianhydride; 4- (2,3-dicarboxyphenoxy) -4 '- (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride; 1,3-bis (2,3-dicarboxyphenoxy) benzene dianhydride; 1,4-bis (2,3-dicarboxyphenoxy) benzene dianhydride; 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride; 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride; 3,3 ', 4,4'-diphenyltetracarboxylic acid dianhydride; 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride; Naphthalic acid dianhydrides such as 2,3,6,7-natutanic dianhydride and the like; 3,3 ', 4,4'-biphenylsulfonic acid tetracarboxylic acid dianhydride; 3,3 ', 4,4'-biphenyl ether tetracarboxylic acid dianhydride; 3,3 ', 4,4'-dimethyldiphenylsilane tetracarboxylic acid dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride; 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride; Bis (phthalic acid) phenylsulfinic acid dianhydride; p-phenylene-bis (triphenylphthalic acid) dianhydride; m-phenylene-bis (triphenylphthalic acid) dianhydride; Bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride; Bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride; 2,2'-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride; 4,4'-oxydiphthalic dianhydride; Pyromellitic acid dianhydride; 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride; 4 ', 4'-bisphenol A dianhydride; Hydroquinone diphthalic acid dianhydride; Bis (3,4-dicarboxyphenoxy) -2,2 ', 3,3'-tetrahydro-3,3,3', 3'-tetramethyl- Lobby [1 H-indene] dianhydride; 7,4'-bis (3,4-dicarboxyphenoxy) -3,3 ', 4,4'-tetrahydro-4,4,4', 4'-tetramethyl- Lobby [2H-1-benzopyran] dianhydride; 1,1'-bis [1- (3,4-dicarboxyphenoxy) -2-methyl-4-phenyl] cyclohexane dianhydride; 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride; 3,3 ', 4,4'-diphenylsulfide tetracarboxylic acid dianhydride; 3,3 ', 4,4'-diphenylsulfoxide tetracarboxylic acid dianhydride; 4,4'-oxydiphthalic dianhydride; 3,4'-oxydiphthalic dianhydride; 3,3'-oxydiphthalic dianhydride; 3,3'-benzophenone tetracarboxylic acid dianhydride; 4,4'-carbonyldiphthalic dianhydride; 3,3 ', 4,4'-diphenylmethane tetracarboxylic acid dianhydride; 2,2-bis (4- (3,3-dicarboxyphenyl) hexafluoropropane dianhydride; (3,3 ' , 4,4'-diphenyl) phenylphosphine tetracarboxylic acid dianhydride, (3,3 ', 4,4'-diphenyl) phenylphosphine oxide tetracarboxylic acid dianhydride, 2,2'-dichloro-3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride, 2,2'-dimethyl-3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 2,2'-dicyano- , 4,4'-biphenyltetracarboxylic acid dianhydride, 2,2'-dibromo-3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2'-diiodo-3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride, 2,2'-ditrifluoromethyl-3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 2,2'-bis (1 Bis (1-trifluoromethyl-2-phenyl) -3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride; , 4'-biphenyltetracarboxylic acid dianhydride, 2,2'-bis (1-trifluoromethyl-3-phenyl) -3,3 ', 4,4'- Bis (1-trifluoromethyl-4-phenyl) -3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride, 2,2'-bis Phenyl-4-phenyl) -3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride, 4,4'-bisphenol A dianhydride, 3,4'-bisphenol A dianhydride, 3,3'-bisphenol A dianhydride, 3,3 ', 4,4'-diphenylsulfoxide tetracarboxylic dianhydride, 4,4'-carbonyldiphthalic dianhydride, 3,3', 4,4'-diphenylmethane tetracarboxylic dianhydride Water, 2,2'-bis (1,3-trifluoromethyl-4-phenyl) -3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, and all the isomers thereof, &Lt; / RTI &gt;

The halo-displacement polymerization process for preparing polyetherimide and polyetherimide sulfone includes, but is not limited to, the reaction of bis (phthalimide) of formula (8)

Wherein R is as described above and X is a nitro group or a halogen. Bis-phthalimide (8) can be prepared, for example, by reacting the corresponding anhydride of formula (9)

(Wherein X is a nitro group or halogen)

The organic diamine of formula (10):

H ₂ NR-NH ₂ (10)

(Where R is as described above)

As shown in Fig.

Illustrative examples of the amine compound of formula (10) are ethylenediamine, propylenediamine, trimethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylene Diamine, 1,12-dodecanediamine, 1,18-octadecanediamine, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 4-methylnonamethylenediamine, Dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 2,2-dimethylpropylenediamine, N-methyl-bis (3-aminopropyl) amine, 3-methoxyhexamethylenediamine, (3-aminopropoxy) ethane, bis (3-aminopropyl) sulfide, 1,4-cyclohexanediamine, bis- (4-aminocyclohexyl) methane, m-phenylenediamine, , 4-diaminotoluene, 2,6-diaminotoluene, m-xylylenediamine, p-xylylenediamine Dimethyl-1,3-phenylene-diamine, 5-methyl-4,6-diethyl-1,3-phenylene-diamine, benzidine, 3,3'-dimethyl (2-chloro-4-amino-3,5-diethylphenyl) methane, bis (4-aminophenyl) methane, bis (P-amino-t-butylphenyl) ether, bis (pb-methyl-o-aminophenyl) benzene, bis (4-aminophenyl) ether, and 1,3-bis (3-aminopropyl) tetramethyldisiloxane. do. Mixtures of these amines may also be used. Exemplary examples of amine compounds of formula (10) containing sulfone groups include, but are not limited to, diaminodiphenylsulfone (DDS) and bis (aminophenoxyphenyl) sulfone (BAPS). In addition, a combination including any of the above-mentioned amines may be used.

The polyetherimide can be synthesized by the reaction of a bis (phthalimide) 8 with an alkali metal salt of a dihydroxy-substituted aromatic hydrocarbon of the formula HO-V-OH in the presence or absence of a phase transfer catalyst, wherein V Is as described above. Suitable phase transfer catalysts are disclosed in U.S. Patent 5,229,482. Specifically, a combination of a dihydroxy-substituted aromatic hydrocarbon bisphenol such as bisphenol A, or an alkali metal salt of bisphenol and an alkali metal salt of another dihydroxy-substituted aromatic hydrocarbon may be used.

In one embodiment, the polyetherimide comprises structural units of formula (5) wherein each R is independently a mixture comprising p-phenylene or m-phenylene or at least one of the foregoing, T is Wherein the divalent bond of the -OZO- group is in the 3,3 'position and Z is a 2,2-diphenylene propane group (bisphenol A group). Furthermore, polyetherimide sulfone comprising the structural unit of formula (6), at least 50 mole% of the R groups is a formula (4), wherein Q is -SO ₂ -, and the remaining R groups are independently phenyl p- Phenylene or a combination comprising at least one of the foregoing, T is a group of the formula -OZO-, wherein the divalent bond of the -OZO- group is in the 3,3 'position, Z is 2, 2-diphenylene propane group.

The polyetherimide and polyetherimide sulfone may be used alone or in combination with each other and / or with the remainder of the polymeric materials disclosed in making the polymeric components of the present invention. In one embodiment, only polyetherimide is used. In other embodiments, the weight ratio of polyetherimide: polyetherimide sulfone can be from 99: 1 to 50:50.

The polyetherimide may have a weight average molecular weight (Mw) of 5,000 to 100,000 grams (g / mole) as measured by gel permeation chromatography (GPC). In some embodiments, Mw can be from 10,000 to 80,000. The molecular weight as used herein refers to the absolute weight average molecular weight (Mw).

The polyetherimide may have an intrinsic viscosity (dl / g) of at least 0.2 per gram as measured in m-cresol at 25 占 폚. Within this range, intrinsic viscosity can be from 0.35 to 1.0 dl / g when measured in m-cresol at 25 占 폚.

The polyetherimide may have a glass transition temperature of greater than 180 DEG C, specifically 200 DEG C to 500 DEG C, as measured using a Differential Scanning Calorimeter (DSC) in accordance with ASTM Test D3418. In some embodiments, the polyether imide has a glass transition temperature of from 240 to 350 &lt; 0 &gt; C.

The polyetherimide may have a melt index (g / min) of from 0.1 to 10 grams per minute as measured by the American Society for Testing and Materials (ASTM) DI 238 at 340 to 370 ° C using a weight of 6.7 kilograms (kg).

The alternative halo-displacement polymerization process for preparing a polyetherimide, for example a polyetherimide having structure (1), is a process called the chloro-displacement process (X is Cl in equation (8)). The chloro-displacement process is illustrated as follows: 4-Chlorophthalic anhydride and meta-phenylenediamine are reacted in the presence of a sodium phenylphosphinate catalyst to yield the bischlorophthalimide of meta-phenylenediamine ( CAS No. 148935-94-8). The bischlorophthalimide is then polymerized by ortho-dichlorobenzene or anisole solvent in the presence of a catalyst by chloro-displacement reaction with di-sodium salt of BPA. Also, a mixture of 3-chloro and 4-chlorophthalic anhydride can be used to provide a mixture of isomeric bischlorophthalimides, which can be polymerized by chloro-displacement with the sodium salt of BPA as described above have.

The siloxane polyetherimide may comprise a polysiloxane / polyetherimide block or random copolymer having a siloxane content of less than 40 weight percent (wt%) based on the total weight of the block copolymer. The block copolymer comprises a siloxane block of formula (I): &lt; RTI ID = 0.0 &gt;

Wherein R ⁶ is substituted or unsubstituted ^1- having 5 to 30 carbon atoms independently, at each occurrence, saturated, unsaturated, or aromatic monocyclic group, a substituted or unsubstituted having from 5 to 30 carbon atoms, saturated, unsaturated, or aromatic A substituted or unsubstituted alkyl group having 1 to 30 carbon atoms and a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, V is selected from the group consisting of substituted or unsubstituted , A saturated, unsaturated, or aromatic monocyclic and polycyclic group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, and at least one of the aforementioned linkers , G is from 1 to 30, and d is from 2 to 20. Commercially available siloxane polyetherimides are available from SABIC Innovative Plastics under the brand name SILTEM ^* ( ^* the trade name of SABIC Innovative Plastics IP BV).

The polyetherimide resin may have a weight average molecular weight (Mw) within a range having a lower limit and / or an upper limit. The range may include or exclude lower and / or upper limits. The lower limit and / or the upper limit is 5000, 6000, 7000, 8000, 9000, 10000, 11000, 12000, 13000, 14000, 15000, 16000, 17000, 18000, 19000, 20000, 21000, 22000, 23000, 24000, 25000, 27000, 28000, 29000, 30000, 31000, 32000, 33000, 34000, 35000, 36000, 37000, 38000, 39000, 40000, 41000, 42000, 43000, 44000, 45000, 46000, 47000, 48000, 49000, 62000, 63000, 64000, 65000, 66000, 67000, 68000, 69000, 700000, 71000, 72000, 73000, 74000, 75000, 76000, 97000, 98000, 99000, 100000, 101000, 99000, 88000, 89000, 900000, 91000, 92000, 93000, 94000, 102000, 103000, 104000, 105000, 106000, 107000, 108000, 109000 and 110000 daltons. For example, the polyetherimide resin may have a weight average molecular weight (Mw) of 5,000 to 100,000 daltons, 5,000 to 80,000 daltons, or 5,000 to 70,000 daltons. The primary alkylamine modified polyether imide will have lower molecular weight and higher melt flow than the unmodified initial polyetherimide.

Polyetherimide resins are described, for example, in U.S. Patent Nos. 3,875,116; 6,919, 422 and 6,355, 723, for example, U.S. Patent 4,690,997; 4,808,686, polyetherimide sulfone resins disclosed in U.S. Patent No. 7,041,773, and combinations thereof, each of which is incorporated herein in its entirety.

The polyetherimide resin may have a glass transition temperature within a range having a lower limit and / or an upper limit. The range may include or exclude lower and / or upper limits. The lower and / or upper limits may be selected from the ranges of 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, It can be selected from the road. For example, the polyetherimide resin may have a glass transition temperature (Tg) of greater than 200 degrees Celsius.

The polyetherimide resin may have substantially no benzyl group (less than 100 ppm). The polyetherimide resin may not have a benzyl group. The polyetherimide resin may have a benzylic proton in an amount of 100 ppm or less. In one embodiment, the amount of both benzylic groups is in the range of more than 0 to less than 100 ppm. In another embodiment, the amount of both benzylic groups is undetectable.

The polyetherimide resin may be substantially free of halogen atoms (less than 100 ppm). The polyetherimide resin may not have a halogen atom. The polyetherimide resin may have an amount of halogen atoms of less than 100 ppm. In one embodiment, the amount of halogen atoms ranges from greater than 0 to less than 100 ppm. In other embodiments, the amount of halogen atoms is undetectable.

In one embodiment, the electrolyte 108 may comprise a molten salt and / or a lithium salt. By way of example, a lithium battery electrolyte may have a low lithium ion conductivity and a viscosity low enough to provide high penetration into the electrode or separator. In one embodiment, the electrolyte 108 is selected from the group consisting of lithium tetrafluoroborate (abbreviated as "LiBF ₄ "), lithium hexafluorophosphate (abbreviated as "LiPF ₆ "), lithium hexafluoromethane sulfonate, lithium bis (trifluoromethane LiDFSI "), lithium dicyanamide (abbreviated as" LiDCA "), lithium trifluoromethane sulfonate (abbreviated as" LiTFS "), and lithium bis (pentafluoroethanesulfonyl) amide LiBETI "). &Lt; / RTI &gt; Other materials and forming processes may also be used.

The cations contained in the above-mentioned molten salts include, but are not limited to, aromatic quaternary ammonium ions such as 1-ethyl-3-methylimidazolium, 1-methyl-3-propylimidazolium, Methylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1-ethyl-3,4-dimethylimidazolium, N-propylpyridinium, Butylpyridinium, N-tert-butylpyridinium and N-tert-pentylpyridinium, and aliphatic quaternary ammonium ions such as N-butyl-N, N, N-trimethylammonium, N- N, N-dimethyl-N-propylammonium, N-methyl-N-propylpyrrolidinium, N N-methylpyrrolidinium, N-methyl-N-methylpyrrolidinium, N-methyl-N-methylpyrrolidinium, -Isopropylpiperidinium, N-butyl-N-methylpiperidinium, N-isobutyl-N-methylpiperidinium, N- methylpiperidinium, sec-butyl-N-methylpiperidinium, N-methoxyethyl-N-methylpiperidinium and N-ethoxyethyl-N-methylpiperidinium. As the nitrogen-containing 5-membered ring of these aliphatic quaternary ammonium ions, the pyrrolidinium ion or the piperidinium ion as the nitrogen-containing 6-membered ring has high reducing resistance which suppresses the side reaction for improving the storage property or cycle performance It is preferable. Other materials and forming processes may also be used.

The anions contained in the molten salt mentioned above are not particularly _{limited, PF 6 -, (PF 3} (C 2 F 5) 3) -, (PF 3 (CF 3) 3) -, BF 4 -, ( _{BF 2 (CF 3) 2)} -, (BF 2 (C 2 F 5) 2) -, (BF 3 (CF 3)) -, (BF 3 (C 2 F 5)) -, (B (COOCOO) ₂₎ - (short for _{"BOB-"), CF 3 SO} 3 - ( stands for _{"Tf-"), C 4 F} 9 SO 3 - ( stands for "Nf-"), ((CF 3 SO 2) 2 N) - (Abbreviated as "TFSI-"), ((C ₂ F ₅ SO ₂ ) ₂ N) - (abbreviated "BETI-"), ((CF ₃ SO ₂ ) (C ₄ F ₉ SO ₂ ) CN) ₂ N) - (abbreviated as "DCA-") and ((CF ₃ SO ₂ ) ₃ C) - and ((CN) ₃ C) -. Of these, _{PF 6 -, (PF 3 (} C 2 F 5) 3) -, (PF 3 (CF 3) 3) -, BF 4 -, (BF 2 (CF 3) 2) -, (BF 2 (C _{2 F 5) 2) -,} (BF 3 (CF 3)) -, (BF 3 (C 2 F 5)) -, Tf-, Nf-, TFSI-, BETI- and ((CF ₃ SO ₂₎ ( C ₄ F ₉ SO ₂ ) N) can be preferably used, and these include F in view of excellent cycle performance. In one embodiment, the electrolyte comprises 0 wt% to 50 wt% ethyl carbonate of the total solvent composition; 0 wt% to 80 wt% dimethyl carbonate of the total solvent composition; And 0 wt% to 80 wt% ethyl methyl carbonate in the total solvent composition.

In use, the positive electrode and the negative electrode are separated from each other by a separator, and are electrically connected to each other by ion movement through the above-mentioned electrolyte. A separator may be formed from a thermoplastic polymer to form a battery comprising an electrolyte having the above-mentioned constitution.

In one embodiment, the thermoplastic polymer phase comprises a thermoplastic resin and a flow modifier. The thermoplastic resin may include, but is not limited to, one or more thermoplastic polymer resins including polyphenylene sulfide and polyimide. In a further aspect, the polyimides used in the disclosed composites include polyamideimides, polyetherimides, and polybenzimidazoles. In a further embodiment, the polyetherimide comprises a melt processible polyetherimide.

Suitable polyetherimides that may be used in the disclosed complexes include, but are not limited to, ULTEM (TM). ULTEM ™ is a family of polyetherimide (PEI) polymers marketed by Saudi Basic Industries Corporation (SABIC). ULTEM (TM) may have elevated heat resistance, high strength and stiffness, and wide chemical resistance. ULTEM ™ as used herein refers to any or all ULTEM ™ polymers included in this family, unless otherwise specified. In a further embodiment, ULTEM (TM) is ULTEM (TM) 1000. In one embodiment, the polyetherimide is described, for example, in U.S. Patent 4,548,997; US 4,629,759; US 4,816,527; US 6,310,145; And US 7,230,066, all of which are incorporated herein by reference in their entirety for specific purposes to disclose the various polyetherimide compositions and methods.

In a particular embodiment, the thermoplastic polymer is a polyetherimide polymer having a structure comprising structural units represented by the organic radicals of formula (I): &lt; EMI ID =

Where R is a substituted or unsubstituted bivalent organic radical such as (a) an aromatic hydrocarbon radical having from 6 to 20 carbon atoms and its halogenated derivatives; (b) a straight or branched alkylene radical having from 2 to 20 carbon atoms; (c) a cycloalkylene radical having from 3 to 20 carbon atoms, or (d) a divalent radical of formula (II):

Wherein Q is a single bond, -O-, -S-, -C (O ) -, -SO 2 -, -SO-, -CyH 2 y- (y is an integer of 1 to 5), and perfluoro Selected from the group consisting of halogenated derivatives thereof including alkylene groups; T is -O- or a group of the formula -OZO-, wherein the divalent bond of the -O- or -OZO- group is in the 3,3 ', 3,4', 4,3 'or 4,4' position, Z includes, but is not limited to, a divalent radical of formula (III)

Wherein the polyether imide contained by formula (I) has a Mw of at least 40,000.

In a further embodiment, the polyetherimide polymer may be a copolymer, which further comprises a polyimide structural unit of formula (IV) in addition to the etherimide unit described above:

Wherein R is as previously defined for formula (I), and M includes, but is not limited to, a radical of formula (V):

In a further embodiment, the thermoplastic resin is a polyetherimide polymer having a structure represented by the formula:

Wherein the polyetherimide polymer has a molecular weight of at least 40,000 daltons, 50,000 daltons, 60,000 daltons, 80,000 daltons, or 100,000 daltons.

The polyetherimide polymer comprises an aromatic bis (ether anhydride) of formula (VI) and:

The organic diamine of formula (IX):

H ₂ NR-NH ₂ (VII),

, &Lt; / RTI &gt; which may be prepared by methods known to those skilled in the art,

Where T and R are defined as described above in formula (I).

Exemplary non-limiting examples of aromatic bis (ether anhydrides) of formula (VI) include 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl ether dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) benzophenone dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride; 2,2-bis [4- (2,3-dicarboxyphenoxy) phenyl] propane dianhydride; 4,4'-bis (2,3-dicarboxyphenoxy) diphenyl ether dianhydride; 4,4'-bis (2,3-dicarboxyphenoxy) diphenylsulfide dianhydride; 4,4'-bis (2,3-dicarboxyphenoxy) benzophenone dianhydride; 4,4'-bis (2,3-dicarboxyphenoxy) diphenylsulfone dianhydride; 4- (2,3-dicarboxyphenoxy) -4 '- (3,4-dicarboxyphenoxy) diphenyl-2,2-propane dianhydride; 4- (2,3-dicarboxyphenoxy) -4 '- (3,4-dicarboxyphenoxy) diphenyl ether dianhydride; 4- (2,3-dicarboxyphenoxy) -4 '- (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride; 4 - (3,4-dicarboxyphenoxy) benzophenone dianhydride and 4- (2,3-dicarboxyphenoxy) -4 '- (3, 4-dicarboxyphenoxy) diphenylsulfone dianhydride, as well as various mixtures thereof.

The bis (ether anhydride) can be prepared by hydrolysis and subsequent dehydration of the reaction product of the phenyl nitrile substituted with nitro and the metal salt of the dihydric phenol compound in the presence of a bipolar aprotic solvent. Useful classes of aromatic bis (ether anhydrides) represented by formula (VI) above include, but are not limited to, compounds wherein T is of formula (VIII)

The ether linkages are, for example, advantageously in the 3,3 ', 3,4', 4,3 ', or 4,4' position, mixtures thereof, and Q is as defined above.

Some diamino compounds may be used in the preparation of polyimides and / or polyetherimides. Exemplary non-limiting examples of suitable diamino compounds of formula (VII) are ethylenediamine, propylenediamine, trimethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, But are not limited to, methylene diamine, decamethylene diamine, 1,12-dodecanediamine, 1,18-octadecanediamine, 3-methylheptamethylene diamine, 4,4- dimethylheptamethylene diamine, But are not limited to, methylenediamine, 2,5-dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 2,2-dimethylpropylenediamine, N-methyl-bis (3-aminopropyl) amine, 3-methoxyhexamethylenediamine, (3-aminopropoxy) ethane, bis (3-aminopropyl) sulfide, 1,4-cyclohexanediamine, bis- (4-aminocyclohexyl) Phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, m-xylenes Diamine, p-xylylenediamine, 2-methyl-4,6-diethyl-1,3-phenylene-diamine, 5-methyl- , 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 1,5-diaminonaphthalene, bis (4-aminophenyl) methane, bis Bis (p-amino-t-butylphenyl) ether, bis (p-methyl-o Aminophenyl) sulfone, bis (4-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, Bis (4-aminophenyl) ether and 1,3-bis (3-aminopropyl) tetramethyldisiloxane. Mixtures of these compounds may also be present. The beneficial diamino compounds are aromatic diamines, especially m- and p-phenylenediamines and mixtures thereof.

In a further embodiment, the polyetherimide resin comprises structural units according to formula (I) wherein each R is independently p-phenylene or m-phenylene or a mixture thereof and T is selected from the group consisting of It is a radical:

In various embodiments, the reaction may be carried out using a solvent such as o-dichlorobenzene, m-cresol / toluene, etc., whereby the reaction between the anhydride of formula (VI) and the diamine of formula (VII) Lt; / RTI &gt; The polyetherimide can also be prepared by melt polymerization of an aromatic bis (ether anhydride) of formula (VI) and a diamine of formula (VII) by heating the mixture of starting materials at elevated temperature with stirring at the same time. The melt polymerization may be carried out at a temperature of from 200 캜 to 400 캜. Chain terminators and branching agents can also be used in the reaction. The polyetherimide polymer can be prepared from the reaction of an aromatic bis (ether anhydride) with an organic diamine, wherein the diamine is present in the reaction mixture in an amount not exceeding 0.2 mole, advantageously less than 0.2 mole excess. Under these conditions, the polyetherimide resin is less than 15 microequivalents per gram (μeq / g) in one embodiment, as determined by titration with a solution of 33 weight percent (wt%) hydrobromic acid in chloroform solution in cold acetic acid And in other embodiments less than 10 &lt; RTI ID = 0.0 &gt; eq / g. &Lt; / RTI &gt; The acid labile group is essentially due to the amine end groups in the polyetherimide resin.

In a further embodiment, the polyetherimide resin has a weight average molecular weight (Mw) of at least 24,000 to 150,000 grams (g / mole) per mole when measured by gel permeation chromatography using polystyrene standards. In another further aspect, the thermoplastic resin may have a molecular weight of at least 20,000 daltons, 40,000 daltons, 50,000 daltons, 60,000 daltons, 80,000 daltons, 100,000 daltons, or 120,000 daltons. In yet another further aspect, the thermoplastic resin may have a molecular weight of at least 40,000 daltons. In yet another further aspect, the thermoplastic resin may have a molecular weight of at least 45,000 Daltons. In yet another further aspect, the thermoplastic resin may have a molecular weight of at least 50,000 Daltons. In yet another further aspect, the thermoplastic resin may have a molecular weight of at least 60,000 Daltons. In yet another further aspect, the thermoplastic resin may have a molecular weight of at least 70,000 daltons. In yet another further aspect, the thermoplastic resin may have a molecular weight of at least 100,000 daltons.

In a further embodiment, the thermoplastic resin may comprise a polyetherimide polymer having a molecular weight of at least 40,000 daltons, 50,000 daltons, 60,000 daltons, 80,000 daltons, or 100,000 daltons. In another further embodiment, the polyetherimide polymer has a molecular weight of at least dalton, 40,000 daltons or 50,000 daltons. In yet another further embodiment, the polyetherimide polymer has a molecular weight of at least 40,000 daltons. In yet another further embodiment, the polyetherimide polymer has a molecular weight of at least 50,000 Daltons. In yet another further embodiment, the polyetherimide polymer has a molecular weight of at least 60,000 daltons. In yet another further embodiment, the polyetherimide polymer has a molecular weight of at least 70,000 daltons. In yet another further embodiment, the polyetherimide polymer has a molecular weight of at least 100,000 daltons.

In one embodiment, liquid induced phase separation (LIPS) or vapor induced phase separation (VIPS) based on ULTEM ™ CRS 5000 resin from SABIC may be used to fabricate one or more lithium ion battery separators. As an example, LIPS or VIPS can be used to fabricate ULTEM (TM) CRS 5000 porous separator films with tunable pore structure, which is well suited for battery separator applications. This process is versatile with respect to the porosity, pore size and thickness obtained, and therefore is versatile in the final performance of the separator in an actual electrochemical cell environment.

Example

The following examples are presented to provide those of ordinary skill in the art with a complete disclosure and description of the manner in which the compounds, compositions, articles, apparatus and / or methods claimed herein are made and evaluated, and are provided by way of illustration only, There is no intention to restrict. Unless otherwise indicated, parts are parts by weight, temperatures are in ° C or ambient temperature, and pressures are atmospheric or atmospheric pressure approximations.

Example testing process

Solvent resistance test is an electrolytic solution (1: 1: 1 ratio DMC: EMC: EC and 1mol / L LiPF ₆₎ or dimethyl carbonate (DMC), diethyl carbonate (DEC) and from the individual electrolyte solvent of ethylene carbonate (EC) The degree of swelling and / or dissolution of the polymer film was determined. All of the tested samples were thin solid films with thicknesses of 50-100 microns. Commercial Celgard ^® 2500 (polypropylene-based) and Tonen V25CGD (polyethylene-based) separators were used as control samples. The detailed procedure for solvent resistance testing using an electrolyte solution is as follows:

1. Prepare 9 replicate samples (thin film) for each material type.

2. Dry all samples in a vacuum according to the typical drying procedure as suggested by the material supplier.

3. Record the starting weight of the dry sample. The electronic balance resolution is 0.00001 grams, and the weight of each individual sample exceeds 0.02 grams, whereby the accuracy is at least +/- 0.05%.

4. Immerse each individual sample in a separate sealed glass container in an excess of electrolyte (sample is completely covered). This process occurs glob-box in an argon atmosphere to protect the electrolyte solution.

5. Store all containers in a heating mantle at 55 ± 2 ° C in a glove-box (argon atmosphere), and take samples out after 21 days.

6. After removing the sample from the solution, rinse the sample according to the following procedure to remove residual solvent and salt residue on the sample surface:

- Ultrasonic rinse in DMC for 2 minutes and rinse twice in DMC

- rinsing in ethanol (3 times)

- Flowing DI water wash

The rinsing process was verified by evaluating commercial separators and successfully removed all organic solvents and lithium salts.

7. To remove the residual electrolyte on the surface of the sample, wipe the wet sample dry with a cloth or tissue and record the weight as wet weight.

8. The sample was vacuum dried at 110 DEG C for 48 hours. The PP and PE samples were dried at 60 DEG C for 24 hours. After drying the ULTEM ™ CRS 5001 film sample at 110 ° C. for 48 hours, the weight still increased, suggesting strong interaction with the electrolyte solvent. Thus, the ULTEM ™ CRS 5001 sample was further dried at 200 ° C. for 24 hours, with no additional weight change observed. The remaining film samples were dried at 110 [deg.] C for 48 hours.

9. Record the weight of the sample as dry weight immediately after removal from the drying oven.

10. The normalized dry weight was calculated by dividing the dry weight by the initial weight. The normalized wet weight was calculated by dividing the wet weight by the initial weight.

The detailed procedure for solvent resistance testing with individual electrolyte solvents is as follows:

1. Prepare 9 replicate samples (thin film) for each material type.

2. All samples were dried in a vacuum according to the typical drying procedure as suggested by the material suppliers.

3. Record the starting weight of the dry sample. The electronic balance resolution is 0.00001 grams, and the weight of each individual sample exceeds 0.02 grams, whereby the accuracy is at least +/- 0.05%.

4. Immerse each individual sample in a separate sealed glass container in an excess of solvent (completely covered by the sample).

5. Store all vessels at 55 ± 2 ° C in a water bath, and remove samples 21 days later.

6. To remove residual solvent from the surface of the sample, wipe the wet sample dry with a cloth or tissue and record the weight as wet weight.

7. The sample was vacuum dried at 110 DEG C for 48 hours. The PP and PE samples were dried at 60 DEG C for 24 hours. The remaining samples were dried under vacuum at &lt; RTI ID = 0.0 &gt; 110 C &lt; / RTI &gt; for three days under vacuum at 150 C for one day.

8. The normalized dry weight was calculated by dividing the dry weight by the initial weight. The normalized wet weight was calculated by dividing the wet weight by the initial weight.

The wettability of the different polymers was evaluated by contact angle measurement using an electrolyte solution (1: 1: 1 ratio of DMC: EMC: EC and 1 mol / L LiPF ₆ ) or individual alkyl carbonate solvents. The contact angle was measured according to a standard procedure (e.g., through a Young's modulus or similar method), where the mathematical notation was fitted to the shape of the droplet and the slope of the tangent to the droplet in the liquid-solid-vapor (LSV) . Each sample was measured at least 5 times and the contact angle recorded 5 seconds after the droplet dispensing on the surface, unless otherwise noted.

Thermomechanical analysis (TMA) is typically used to characterize the high temperature melt integrity (HTMI) of a setter in accordance with the ASA / TM - 2010-216099 test method. TMA is used to keep the separator under constant and low load, and strain (elongation) is measured as a function of temperature. At temperatures where the separator loses mechanical integrity, the elongation increases dramatically. Typically, the shrinkage starting temperature (2% shrink temperature), the deformation temperature (5% deformation temperature) and the breaking temperature (the temperature at which the material is broken) are recorded and the hot melt integrity is defined as the deformation temperature. The high temperature melt integrity (HTMI) of the separator is defined as a 5% strain temperature. TA Instrument Q800 DMA was used under film tension setting. 10 mm long and 3 mm wide films were tested. The sample is held at a constant 0.02 N load while raising the temperature to 5 캜 / min until the sample breaks. The experimental variables are as follows:

a. Test: Temperature rise / controlled force

b. Preload force: 0.02N

c. Starting temperature: 30 ℃

d. Final temperature: 300 ° C (or sample break)

e. Ascent Rate: 5 ℃ / min

In one embodiment, a 2016 coin cell was used as a test vehicle to determine the ionic conductivity. ["NASA / TM-2010- 216099]. A lithium metal slice (99.9% pure lithium metal) purchased from WISDOM OPTOELECTRONIC TECHNOLOGY CO., LTD. Was used as the electrode. Electrochemical Impedance Spectroscopy (EIS) was used to test the cell resistance using a VMP2 multipotentiostat from BioLogic Science Instruments. The non-conductivity is calculated according to Ohm's law:

Non-Conductivity = Film Thickness / (Separator Resistance * Test Area)

The film thickness was measured in micrometers and the separator resistance was read from an EIS nyquist plot and the test area was determined by electrode size (diameter 15.6 mm).

For the cycling test, a LiFePO ₄ cathode was purchased from BYD and the graphite anode was purchased from MTI Co. Lt; / RTI &gt; 2016 Coin Cell Ingredients by Shenzhen Kejingstar Tech Co. Lt; / RTI &gt; The electrolyte used was Shenzhen Capchem Tech Co. Lt; / RTI &gt; The test procedure for the LiFePO ₄ 2016 coin cell is as follows:

1. Formation cycle: Constant current charge at 0.3mA up to 3.8V of voltage hits; Constant voltage charge at 3.8V until current trip to 0.075mA; 1 minute open circuit; Constant current discharge at -0.3mA up to 2.5V voltage hits; Constant current charge at 1.5mA until voltage hits 3.8V; Constant voltage charge at 3.8 V until current trip to 0.075 mA; Open circuit voltage monitor for 24h and capacity record as 100%.

2. Charge / Discharge Cycle: constant current charge at 1.5mA up to 3.8V of voltage hits; Constant voltage charge at 3.8V until current trip to 0.075mA; 1 minute open circuit; Constant current discharge at -1.5 mA until voltage hits 2.5 V; 1 minute open circuit; Repeat the cycle for 1200 subsequent cycles. Record the discharged capacity. The ratio of the discharged capacity to the discharged capacity during the formation cycle is recorded as the capacity retention in percentage.

material

In one embodiment, a plurality of materials illustrated below were tested:

The electrolyte used in this study is LBC3015B purchased from Capchem. It is a mixture of ethylene carbonate (EC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC) and LiPF ₆ . The EC, DMC and EMC ratios were 1: 1: 1 and the LiPF ₆ concentration was 1 mol / L.

Solid film characteristics

[Table A]

In the electrolyte solution,

The data in Table A indicate that the polyethylene and polypropylene separator films have excellent solvent resistance to electrolyte solutions (1: 1: 1 EC: DMC: EMC and 1 mol / L LiPF ₆ ) (E.g., 90% to 101%, 91% to 101%, 92% to 101%, 93% to 101%, 94% to 101%, 95% to 101%, 96% To 101%, 98% to 101%, 99% to 101%, and 100% to 101%). The normalized dry weight was calculated by dividing the weight of the sample after soaking for 21 days in dry weight, i. E., 55 &lt; 0 &gt; C in solution, followed by drying to remove all solvent, . In addition, these materials have low swelling (normalized wet weight of about 100%). The normalized wet weight was calculated by dividing the wet weight, i.e. the weight of the sample after soaking for 21 days in solution at 55 占 폚 without drying the sample, by the initial weight of the sample before soaking in the starting weight, i.e. solution.

Comparative examples of amorphous resins demonstrate significant dissolution of the polymer in the electrolyte solution (normalized dry weight < 90%, mostly completely dissolved).

The data obtained for the ULTEM ™ CRS 5001 resin indicates that the ULTEM ™ CRS 5001 resin does not significantly dissolve in the electrolyte solution as evidenced by the normalized dry weight> 90% It means having excellent content. This is important for the application of ULTEM ™ CRS 5001 in battery separator applications because the dissolution of the polymer in the electrolyte significantly changes the physical structure of the separator, such as pore size and thickness. Further, the significant dissolution of the separator in the electrolyte solution can change the ion transport characteristics through the separator and the electrolyte, for example, by changing the porous structure of the separator and / or by changing the viscosity of the electrolyte solution. In addition, ULTEM (TM) CRS 5001 resin exhibits limited swelling (normalized wet weight 110%). The limited swelling of the separator in the electrolyte solution is important because the significant swelling of the separator by the electrolyte solution can significantly change the physical performance of the separator, for example by changing mechanical stiffness and strain temperature.

The solvent resistance of the polymer is typically related to the relative solubility parameter ([delta]) difference [C. M. Hansen, Hansen Solubility Parameters - A User's Handbook, 2nd edition). When the solubility parameters of the polymer and solvent are slightly different (delta), the polymer can typically dissolve in the solvent. Table B shows the solubility parameters of the typical electrolyte components (δt), dispersibility (δd), polarity (δp) and hydrogen (δh).

[Table B]

The solubility parameter of the carbonate solvent mainly used in the electrolyte composition

In addition, the solvent resistance of ULTEM ™ 1010, ULTEM ™ CRS 5011 and ULTEM ™ CRS 5001 polymer films was tested for individual electrolyte solvents. Based on Table B, dimethyl carbonate (DMC), diethyl carbonate (DEC) was used and ethyl carbonate (EC), which covers the broadest range of solvent solubility parameter (18.0 to 29.6 MPa ^1/2).

[Table C]

In individual electrolyte solvents,

The data in Table C indicate that the solvent resistance of ULTEM (TM) CRS 5001 and ULTEM (TM) CRS 5011 is superior for all individual electrolyte solvents (100 ± 1% normalized dry weight) (I.e., normalized dry weight > 90%) of ULTEMTM CRS 5001 and ULTEMTM CRS 5011 over time (when mixed with EC, DMC and DEC). ULTEM ™ 1010 exhibited significant dissolution / deformation in the solvent, in which case quantitative weight analysis was not possible.

[Table D]

High temperature melt integrity

Table D shows that solid ULTEM ™ 1010 and ULTEM ™ CRS 5001 films provide excellent high temperature melt integrity (HTMI) performance with very high 5% strain temperature exceeding 230 ° C.

[Table E]

Contact angle (measured in electrolyte solution)

Table E shows that the solid ULTEM ™ 1010 and ULTEM ™ CRS 5001 films exhibit an electrolyte solution (1: 1: 1 EC: DMC: EMC and 1 mol / L LiPF ₆ ), as suggested by an extremely low contact angle value (<Lt; RTI ID = 0.0 > wettability &lt; / RTI &gt; These contact angle values are significantly lower than values obtained for solid PP and UHMWPE films (typically &gt; 35 DEG).

[Table F]

Contact angle (measured in individual solvents)

Table F shows that the contact angle of the solid PP film is relatively high over the entire range of solvent compositions tested (typically > 30 DEG). On the other hand, ULTEM ™ 1010 and ULTEM ™ CRS 5001 solid films exhibit very low contact angles (typically <15 °) over a very wide composition range of solvents, suggesting superior wettability of the film by the solution. ULTEM ™ 1010 and ULTEM ™ CRS 5001 films exhibit a contact angle of less than 30 °, which is significantly less than the comparable PP 621P.

Characteristics of porous film

The porous film can be produced using various methods. As an example, the porous film can be formed by a solvent casting method, by stretching the extruded film and / or by washing the solute in an extruded film. Other methods for forming the separator may also be used. As a further example, a porous film having a total porosity ranging from 45 to 75% may be produced. Other ranges and porosities may also be used.

A porous ULTEM ™ CRS 5001 separator was prepared by solvent casting method. The ULTEM (TM) CRS 5001 polymer was dissolved in a solvent mixture of 4-chloro-2-methyl-phenol / p-cresol (1: 1 w / w) at 120 占 폚. The polymer concentration in the dope solution was 17%. The dope solution was cooled to room temperature and then cast onto a glass substrate with a bird applicator (slot size: 50 mu m) at room temperature. The cast film was immersed in a tetrahydrofuran (THF) bath overnight and then dried at 120 DEG C under vacuum. Figure 2 shows a representative form (cross-section) of a solvent cast ULTEM CRS 5001 separator (see Example 20).

[Table G]

Contact angle (measured in electrolyte solution)

Table G shows that the contact angles of the Celgard and Tonen separators are high, typically 40 to 50 degrees after 5 seconds. Even after the electrolyte droplets contact the separator for 30 seconds, the contact angle is maintained above 35 °, suggesting poor wettability of the Celgard and Tonen separators by the electrolyte solution. However, the ULTEM ™ CRS 5001 separator produced exhibits an extremely low contact angle of <10 ° after 30 seconds. After a short contact time of 5 seconds, the contact angle was already 20 ° or less, which means almost immediate wetting of the separator by the electrolyte solution.

[Table H]

Contact angle (measured in individual solvents)

Table H shows that the contact angles of the Celgard and Tonen separators are relatively high over the full range of solvent compositions tested (typically > 25 [deg.]). On the other hand, the ULTEM ™ CRS 5001 separator exhibits an extremely low contact angle (<10 °) over a very wide composition range of solvents, suggesting superior and immediate wetting ability of the separator by the solvent mixture.

[Table I]

High temperature melt integrity

Table I compares the HTMI performance of the ULTEM ™ CRS 5001 separator with that of the Celgard and Tonen separators, while the ULTEM ™ CRS 5001 separator exhibits superior performance with a strain temperature well in excess of 200 ° C, Lt; RTI ID = 0.0 &gt; 160 C. &lt; / RTI &gt; In addition, the break temperature of the ULTEM ™ CRS 5001 separator exceeds 200 ° C, which is a significant improvement over the break temperatures of Celgard and Tonen separators of <170 ° C.

Table J illustrates a comparison of the ionic conductivities of ULTEM ™ CRS 5001 separators and commercial polyolefin separators (Celgard and Tonen). It is evident that the ULTEM ™ CRS 5001 separator contains a similar or higher ionic conductivity than commercial polyolefin separator films. The number in parentheses indicates the standard deviation based on three measurements.

[Table J]

Ion conductivity of separator

Both the ULTEM ™ CRS 5001 separator and the Celgard ™ 2320 separator were tested on a 2016 coin cell. The cathode is LiFePO _4, the anode is lithium metal slice. The electrolyte described above was used. The cycle life was tested at a constant charge and discharge rate of 0.5C. The cycle life over 1200 cycles for two separators is shown in Fig.

Figure 3 shows the discharge capacity retention rate averaged across three cells per separator type using a Celgard 占 2320 and ULTEM 占 CRS 5001 separator. Each of the three cells tested for each separator type is a complete replica. In FIG. 3, the vertical error bars represent the standard deviation of the capacity retention rate of three cells. Although Celgard ™ 2320 is selected as a commercial comparative separator, a similar capacity retention profile was observed, for example, on Celgard ™ 2500. Surprisingly, when comparing capacity retention data, the ULTEM ™ CRS 5001 separator exhibits significantly better cycle performance compared to the Celgard ™ 2320 separator. As an example, the capacity retention rate at 1200 cycles for Celgard ™ 2320 is 52%, while the capacity retention for solvent cast ULTEM ™ CRS 5001 is 79%. In general, the battery industry uses 80% capacity retention as a reliable marker for evaluating battery life. For a LiFePO ₄ / graphite coin cell with a Celgard 2320 separator, the cycle life in this test condition can be equivalent to ~ 250 cycles. Surprisingly, a cell with a ULTEM ™ CRS 5001 separator exhibits a significantly higher cycle life of ~ 1100 cycles.

As shown and described herein, the polyetherimide (PEI) based on para-phenylenediamine (ULTEMTM CRS 5000 series of SABIC) has a high compatibility with electrolyte, a high solvent resistance and a high melt integrity temperature It is an excellent material for battery separator films with a combination of superior performance features. PEI meets critical requirements for battery electrolyte solutions that must be resistant even at elevated temperatures of 55 ° C. In addition, PEI exhibits an extremely low contact angle with respect to the electrolyte solution, which is advantageous for separator wettability and electrolyte retention, thereby reducing the electrolyte filling time during cell preparation and improving cell performance in operation. Separators from PEI based on para-phenylenediamine have very high melt integrity (above 180 DEG C) and a high elastic modulus over the entire range of cell operation. The proposed material is capable of both melting and solution processing into a porous film with a specific ionic conductivity equal or superior to that of a typical commercial polyolefin-based separator. In addition, these PEI separators significantly improve the cycle life of the battery.

Liquid-induced phase separation (LIPS) course

In one embodiment, the solvent-resistant ULTEM ™ CRS 5000 polymer can be dissolved in a phenolic solvent (such as 2-chloro-phenol) at elevated temperatures. Co-solvents that form the solvent and the minimum melting point solvent mixture may be added to maintain the dope solution fluid during casting at room temperature. The porous structure can be formed by soaking the cast wet film in a coagulating bath containing a non-solvent for the polymer and removing the solvent at 120 캜 under vacuum.

In one aspect, a method of making a porous material (e.g., a film, a separator, etc.) comprises providing an injectable polymer solution comprising a chemical resistant polymer in a solvent and forming a porous film from the polymer solution can do. As an example, the formation of a porous film from a polymer solution can include casting a wet film that is wet from the polymer solution. As another example, the formation of a porous film from a polymer solution can include immersing the polymer solution in a coagulating bath comprising a non-solvent for the polymer. In one embodiment, the non-solvent may comprise water, a pyrrolidone-based solvent, acetone, isopropanol, tetrahydrofuran, dichloromethane, dimethylacetate, EDC, DMSO, anisole, ODCB, .

In another embodiment, the polymer may comprise a polyetherimide, polyimide, polyketone, or polyphenylene sulfide, or a combination thereof. By way of example, the polymer comprises a polyetherimide based on para-phenylenediamine.

In one embodiment, the solvent may comprise a phenolic solvent. By way of example, the solvent may be selected from the group consisting of 4-chloro-3-methyl-phenol, 4-chloro-2-methyl-phenol, 2,4- Cresol, p-cresol, 4-methoxy-phenol, catechol, benzoquinone, 2,3-xylenol, 2,6- - xylenol, or resorcinol, or combinations thereof. As a further example, the polymer solution may comprise inorganic particles.

In one embodiment, the porosity of the porous film can be tuned in the range of 10% to 90%. By way of example, the average pore size of the porous film can be tuned to 0.01 탆 to 10 탆. In another embodiment, the stress at a 2% strain offset of the porous film can be varied in the range of 200 to 3000 psi. In a further embodiment, the MacMullin number of the porous film is no greater than 15.

In one embodiment, the porous film can be implemented as a separator. By way of example, the separator may exhibit a 5% strain at temperatures of 180 ° C or higher. As another example, the separator may have an electrolyte contact angle of 30 DEG or less. As a further example, the separator may be resistant to but very compatible with the electrolyte solution.

In one embodiment, the porous film can be used as a substrate for an additional coating (polymer, ceramic) or as a component for a more complex separator configuration (multilayer).

In one embodiment, the energy storage device may comprise a porous film. As an example, the porous film may be disposed as a separator in an electrochemical cell. As another example, the electrochemical cell is a lithium ion battery. As a further example, the electrochemical cell is an electrolytic capacitor.

The following examples are presented to provide those of ordinary skill in the art with a complete disclosure and description of the manner in which the claimed compounds, compositions, articles, apparatus and / or methods are being produced and evaluated and are shown by way of example only, There is no intention to limit. Although efforts have been made to ensure accuracy with respect to numbers (eg, quantity, temperature, etc.), some errors and deviations should be considered. Unless otherwise indicated, parts are parts by weight, temperatures are in ° C or ambient temperature, and pressures are atmospheric or atmospheric pressure approximations.

material

In one embodiment, the ULTEM (TM) CRS 5001 polymer is dissolved in a phenolic solvent (such as 4-chloro-2-methyl-phenol or p-cresol) at elevated temperature and then co- Was added to maintain the dope solution fluid during casting at room temperature. In another embodiment, the ULTEM (TM) CRS 5001 polymer was dissolved in a phenolic solvent (such as 2-chloro-phenol) at elevated temperatures. The porous structure was formed by casting a wet film that was wet on a glass plate, dipping the cast thin film in a coagulating bath containing a non-solvent for the polymer, and removing the residual solvent in the film at 120 캜 under vacuum. It is also possible to cast a thin film wetted on a porous polyethylene film (PE, 8 microns thick, apparent porosity 24%), soak the cast wet film on top of the porous substrate in a coagulation bath containing a non-solvent for the polymer, To remove the residual solvent in the membrane at 60 占 폚 to form a multilayer porous structure.

The apparent porosity of the separator was calculated. The film was cut into circular slices of 19 mm diameter on the die, the sample thickness was measured with a spiral micrometer (Mitutoyo) and weighed on an electrical balance with a +/- 0.05% variance. The apparent porosity is then calculated by the following equation:

Apparent porosity = 1 - Sample gross weight / Resin density x Sample thickness x Sample area

Tensile strength was measured by a TA Instrument Q800 DMA on rectangular (3 x 20 mm) film samples. The measurement method for tensile strength utilizes a film tension clamp in a dynamic mechanical analyzer (DMA) using a strain ramp. The following experimental variables were used:

a. Test: Strain Rise

b. Preloading force: 0.001N

c. Initial strain: 0.5%

d. Isothermal temperature: 30 ° C

e. Final strain: 250%

f. Ascent Rate: 5% / min

g. Ensure that the sample is properly loaded into the film tensile clamp and that all necessary measurements have been made and accurate.

result

Lithium ion battery separators require specific microstructures that can satisfy the balance between mechanical stiffness / strength and ionic conductivity. The conditions used during the phase separation process affect the pore structure and thus the performance of the final separator. The following examples show how the final structure and properties of the separator depend to some extent on the solvent system, polymer concentration and solidification bath used in the phase separation process, using ULTEMTM CRS 5001 (SABIC) as the base resin. Young's modulus (rigidity), ionic conductivity, high-temperature melt integrity (HTMI) and electrolyte wettability of the separator were measured.

Table AA lists the LIPS process variables, which appear to be the most important key factors affecting the final structure of the formed separator. Because of the molecular structure, ULTEM ™ CRS 5001 has unexpected solvent resistance and is therefore less soluble in most common solvents. For this reason, a mixture of chloro-2-methyl-phenol, 2-chloro-phenol and / or p-cresol solvent systems is used to achieve the required injectable polymer system at room temperature at a polymer concentration of 15-20 wt%. The solvents used in the examples of Table AA and mixtures thereof are all liquid at room temperature. The solidification bath (with respect to composition and temperature) plays a key role in controlling the final structure and achieving the desired separator performance. Seven types of coagulation solvents were used at 22 or 40 占 폚, as shown in Table AA.

[Table AA]

LIPS Course Variables

In Example 1, ULTEM (TM) CRS 5001 polymer was dissolved in a solvent mixture of 4-chloro-2-methyl-phenol / p-cresol (1: 1 w / w) at 120 ° C. The polymer concentration in the dope solution was 15%. The dope solution was cooled to room temperature and then cast on a glass substrate with a Bird applicator (slot size: 100 mu m) at room temperature. The cast film was immersed in a methanol bath overnight and then dried at 120 DEG C under vacuum.

In Example 2, ULTEM (TM) CRS 5001 polymer was dissolved in a solvent mixture of 4-chloro-2-methyl-phenol / p-cresol (1: 1 w / w) at 120 ° C. The polymer concentration in the dope solution was 15%. The dope solution was cooled to room temperature and then cast on a glass substrate with a Bird applicator (slot size: 100 mu m) at room temperature. The cast film was immersed in an ethanol bath overnight and then dried at 120 DEG C under vacuum.

In Example 3, ULTEM (TM) CRS 5001 polymer was dissolved in a solvent mixture of 4-chloro-2-methyl-phenol / p-cresol (1: 1 w / w) at 120 ° C. The polymer concentration in the dope solution was 15%. The dope solution was cooled to room temperature and then cast on a glass substrate with a Bird applicator (slot size: 100 mu m) at room temperature. The cast film was immersed overnight in a butanol bath and then dried at 120 캜 under vacuum.

In Example 4, ULTEM (TM) CRS 5001 polymer was dissolved in a solvent mixture of 4-chloro-2-methyl-phenol / p-cresol (5: 1 w / w) at 120 ° C. The polymer concentration in the dope solution was 15%. The dope solution was cooled to room temperature and then cast on a glass substrate with a Bird applicator (slot size: 100 mu m) at room temperature. The cast film was soaked overnight in an isopropanol bath and then dried at 120 DEG C under vacuum.

In Example 5, ULTEM (TM) CRS 5001 polymer was dissolved in a solvent mixture of 4-chloro-2-methyl-phenol / p-cresol (5: 1 w / w) at 120 ° C. The polymer concentration in the dope solution was 15%. The dope solution was cooled to room temperature and then cast on a glass substrate with a Bird applicator (slot size: 100 mu m) at room temperature. The cast film was immersed overnight in a isopropanol / p-cresol (3: 1 ratio) as a coagulation bath. The formed film was rinsed several times with isopropanol and the sample was then dried at 120 DEG C under vacuum.

In Example 6, the ULTEM (TM) CRS 5001 polymer was dissolved in a solvent mixture of 4-chloro-2-methyl-phenol / p-cresol (5: 1 w / w) at 120 ° C. The polymer concentration in the dope solution was 20%. The dope solution was cooled to room temperature and then cast on a glass substrate with a Bird applicator (slot size: 100 mu m) at room temperature. The cast film was soaked overnight in an isopropanol bath and then dried at 120 DEG C under vacuum.

In Example 7, ULTEM (TM) CRS 5001 polymer was dissolved in a solvent mixture of 4-chloro-2-methyl-phenol / p-cresol (5: 1 w / w) at 120 ° C. The polymer concentration in the dope solution was 20%. The dope solution was cooled to room temperature and then cast on a glass substrate with a Bird applicator (slot size: 100 mu m) at room temperature. The cast film was immersed overnight in a isopropanol / p-cresol (3: 1 ratio) as a coagulation bath. The formed film was rinsed several times with isopropanol and the sample was then dried at 120 DEG C under vacuum.

In Example 8, ULTEM (TM) CRS 5001 polymer was dissolved in a solvent mixture of 4-chloro-2-methyl-phenol / p-cresol (1: 1 w / w) at 120 ° C. The polymer concentration in the dope solution was 15%. The dope solution was cooled to room temperature and then cast on a glass substrate with a Bird applicator (slot size: 100 mu m) at room temperature. The cast film was soaked overnight in an isopropanol bath and then dried at 120 DEG C under vacuum.

In Example 9, ULTEM (TM) CRS 5001 polymer was dissolved in a solvent mixture of 4-chloro-2-methyl-phenol / p-cresol (1: 1 w / w) at 120 ° C. The polymer concentration in the dope solution was 15%. The dope solution was cooled to room temperature and then cast on a glass substrate with a Bird applicator (slot size: 100 mu m) at room temperature. The cast film was immersed overnight in a isopropanol / p-cresol (3: 1 ratio) as a coagulation bath. The formed film was rinsed several times with isopropanol and the sample was then dried at 120 DEG C under vacuum.

In Example 10, the ULTEM (TM) CRS 5001 polymer was dissolved in a solvent mixture of 4-chloro-2-methyl-phenol / p-cresol (1: 1 w / w) at 120 ° C. The polymer concentration in the dope solution was 17%. The dope solution was cooled to room temperature and then cast on a glass substrate with a Bird applicator (slot size: 100 mu m) at room temperature. The cast film was soaked overnight in an isopropanol bath and then dried at 120 DEG C under vacuum.

In Example 11, ULTEM (TM) CRS 5001 polymer was dissolved in a solvent mixture of 4-chloro-2-methyl-phenol / p-cresol (1: 1 w / w) at 120 ° C. The polymer concentration in the dope solution was 17%. The dope solution was cooled to room temperature and then cast on a glass substrate with a Bird applicator (slot size: 100 mu m) at room temperature. The cast film was immersed overnight in a isopropanol / p-cresol (3: 1 ratio) as a coagulation bath. The formed film was rinsed several times with isopropanol and the sample was then dried at 120 DEG C under vacuum.

In Example 12, the ULTEM (TM) CRS 5001 polymer was dissolved in a solvent mixture of 4-chloro-2-methyl-phenol / p-cresol (1: 1 w / w) at 120 ° C. The polymer concentration in the dope solution was 17%. The dope solution was cooled to room temperature and then cast on a glass substrate with a bud applicator (slot size: 50 mu m) at room temperature. The cast film was soaked overnight in an ethyl acetate bath and then dried at 120 [deg.] C under vacuum.

In Example 13, the ULTEM (TM) CRS 5001 polymer was dissolved in a solvent mixture of 4-chloro-2-methyl-phenol / p-cresol (1: 1 w / w) at 120 ° C. The polymer concentration in the dope solution was 17%. The dope solution was cooled to room temperature and then cast on a glass substrate with a bud applicator (slot size: 50 mu m) at room temperature. The cast film was immersed in an acetone bath overnight and then dried at 120 캜 under vacuum.

In Example 14, ULTEM (TM) CRS 5001 polymer was dissolved in a solvent mixture of 4-chloro-2-methyl-phenol / p-cresol (1: 1 w / w) at 120 ° C. The polymer concentration in the dope solution was 17%. The dope solution was cooled to room temperature and then cast on a glass substrate with a bud applicator (slot size: 50 mu m) at room temperature. The cast film was immersed in a heptane bath overnight and then dried at 120 [deg.] C under vacuum.

In Example 15, ULTEM (TM) CRS 5001 polymer was dissolved in a solvent mixture of 4-chloro-2-methyl-phenol / p-cresol (1: 1 w / w) at 120 ° C. The polymer concentration in the dope solution was 17%. The dope solution was cooled to room temperature and then cast on a glass substrate with a bud applicator (slot size: 50 mu m) at room temperature. The cast film was immersed in a 1-methyl-2-pyrrolidone (NMP) bath overnight and then dried at 120 DEG C under vacuum.

In Example 16, ULTEMTM CRS 5001 polymer was dissolved in 2-Cl-phenol at 120 占 폚. The polymer concentration in the dope solution was 13%. The dope solution was cooled to room temperature and then cast on a glass substrate with a bud applicator (slot size: 50 mu m) at room temperature. The cast film was immersed in a tetrahydrofuran bath overnight and then dried at 120 DEG C under vacuum.

In Example 17, ULTEMTM CRS 5001 polymer was dissolved in 2-Cl-phenol at 120 &lt; 0 &gt; C. The polymer concentration in the dope solution was 13%. The dope solution was cooled to 40 占 폚 and then cast on a glass substrate with a bird applicator (slot size: 50 占 퐉). The cast film was immersed in a tetrahydrofuran bath overnight. Both the dope / coagulation bath and the glass substrate were maintained at 40 占 폚 during processing. The sample was dried at 120 &lt; 0 &gt; C under vacuum.

In Example 18, ULTEMTM CRS 5001 polymer was dissolved in 2-Cl-phenol at 120 占 폚. The polymer concentration in the dope solution was 13%. The dope solution was cooled to room temperature and then cast on a glass substrate with a bud applicator (slot size: 50 mu m) at room temperature. The cast film was immersed in a tetrahydrofuran / 2-Cl-phenol mixture bath (3: 1 v / v) overnight. The formed film was rinsed several times with THF, and then the sample was dried at 120 DEG C under vacuum.

In Example 19, ULTEMTM CRS 5001 polymer was dissolved in 2-Cl-phenol at 120 占 폚. The polymer concentration in the dope solution was 13%. The dope solution was cooled to 40 占 폚 and then cast on a glass substrate with a bird applicator (slot size: 50 占 퐉). The cast film was immersed in a tetrahydrofuran / 2-Cl-phenol mixture bath (3: 1 v / v) overnight. Both the dope / coagulation bath and the glass substrate were maintained at 40 占 폚 during processing. The formed film was rinsed several times with THF, and then the sample was dried at 120 DEG C under vacuum.

In Example 20, the ULTEM (TM) CRS 5001 polymer was dissolved in a solvent mixture of 4-chloro-2-methyl-phenol / p-cresol (1: 1 w / w) at 120 ° C. The polymer concentration in the dope solution was 17%. The dope solution was cooled to room temperature and then cast on a glass substrate with a bud applicator (slot size: 50 mu m) at room temperature. The cast film was immersed in a tetrahydrofuran bath overnight and then dried at 120 DEG C under vacuum.

In Example 21, ULTEM (TM) CRS 5001 polymer was dissolved in a solvent mixture of 4-chloro-2-methyl-phenol / p-cresol (1: 1 w / w) at 120 ° C. The polymer concentration in the dope solution was 17%. The dope solution was cooled to 40 占 폚 and then cast on a glass substrate with a bird applicator (slot size: 50 占 퐉). The cast film was immersed in a tetrahydrofuran bath overnight. Both the dope / coagulation bath and the glass substrate were maintained at 40 占 폚 during processing. The sample was dried at 120 &lt; 0 &gt; C under vacuum.

In Example 22, ULTEM (TM) CRS 5001 polymer was dissolved in a solvent mixture of 4-chloro-2-methyl-phenol / p-cresol (1: 1 w / w) at 120 ° C. The polymer concentration in the dope solution was 17%. The dope solution was cooled to room temperature and then cast on a glass substrate with a bud applicator (slot size: 50 mu m) at room temperature. The cast film was immersed overnight in a tetrahydrofuran / p-cresol mixture bath (3: 1 v / v). The formed film was rinsed several times with THF, and then the sample was dried at 120 DEG C under vacuum.

In Example 23, ULTEM (TM) CRS 5001 polymer was dissolved in a solvent mixture of 4-chloro-2-methyl-phenol / p-cresol (1: 1 w / w) at 120 ° C. The polymer concentration in the dope solution was 17%. The dope solution was cooled to 40 占 폚 and then cast on a glass substrate with a bird applicator (slot size: 50 占 퐉). The cast film was immersed overnight in a tetrahydrofuran / p-cresol mixture bath (3: 1 v / v). Both the dope / coagulation bath and the glass substrate were maintained at 40 占 폚 during processing. The formed film was rinsed several times with THF, and then the sample was dried at 120 DEG C under vacuum.

In Example 24, ULTEM (TM) CRS 5001 polymer was dissolved in a solvent mixture of 4-chloro-2-methyl-phenol / p-cresol (1: 1 w / w) at 120 ° C. The polymer concentration in the dope solution was 17%. The dope solution was cooled to room temperature and then cast onto a porous polyethylene substrate (8 micron thick) with a Bird applicator (slot size: 50 mu m). The cast film was soaked overnight in an ethyl acetate bath and then dried at 60 [deg.] C under vacuum.

In Example 25, ULTEM (TM) CRS 5001 polymer was dissolved in a solvent mixture of 4-chloro-2-methyl-phenol / p-cresol (1: 1 w / w) at 120 ° C. The polymer concentration in the dope solution was 17%. The dope solution was cooled to room temperature and then cast onto a porous polyethylene substrate (8 micron thick) with a Bird applicator (slot size: 50 mu m). The cast film was immersed in an acetone bath overnight and then dried at 60 DEG C under vacuum.

In Example 26, ULTEM (TM) CRS 5001 polymer was dissolved in a solvent mixture of 4-chloro-2-methyl-phenol / p-cresol (1: 1 w / w) at 120 ° C. The polymer concentration in the dope solution was 17%. The dope solution was cooled to room temperature and then cast onto a porous polyethylene substrate (8 micron thick) with a Bird applicator (slot size: 50 mu m). The cast film was immersed in a THF bath overnight and then dried at 60 ° C under vacuum.

In Example 27, ULTEMTM CRS 5001 polymer was dissolved in 2-Cl-phenol at 120 &lt; 0 &gt; C. The polymer concentration in the dope solution was 13%. The dope solution was cooled to 40 占 폚 and then cast onto a porous polyethylene substrate (8 micron thick) with a Bird applicator (slot size: 25 占 퐉). The cast film was immersed in a 3: 1 (v / v) bath of tetrahydrofuran / 2-Cl-phenol overnight. Both the dope / coagulation bath and the glass substrate were maintained at 40 占 폚 during processing. The formed film was rinsed several times with THF and the sample was then dried at 60 DEG C under vacuum.

In Example 28, ULTEM (TM) CRS 5001 polymer was dissolved in 2-Cl-phenol at 120 占 폚. The polymer concentration in the dope solution was 13%. The dope solution was cooled to 40 占 폚 and then cast onto a porous polyethylene substrate (8 micron thick) with a bud applicator (slot size: 50 占 퐉). The cast film was immersed in a 3: 1 (v / v) bath of tetrahydrofuran / 2-Cl-phenol overnight. Both the dope / coagulation bath and the glass substrate were maintained at 40 占 폚 during processing. The formed film was rinsed several times with THF and the sample was then dried at 60 DEG C under vacuum.

In Example 29, ULTEM (TM) CRS 5001 polymer was dissolved in 2-Cl-phenol at 120 &lt; 0 &gt; C. The polymer concentration in the dope solution was 13%. The dope solution was cooled to 40 占 폚 and then cast onto a porous polyethylene substrate (8 micron thick) with a Bird applicator (slot size: 75 占 퐉). The cast film was immersed in a 3: 1 (v / v) bath of tetrahydrofuran / 2-Cl-phenol overnight. Both the dope / coagulation bath and the glass substrate were maintained at 40 占 폚 during processing. The formed film was rinsed several times with THF and the sample was then dried at 60 DEG C under vacuum.

4 to 25 show scanning electron microscope (SEM) images showing the cross-sectional shapes of the prepared porous separator films of Examples 1 to 14 and 16 to 23, respectively. In particular, ULTEMTM CRS 5001 forms a clear, dense film when immersed in NMP (Example 15), so this case was not included in further analysis. Figures 43 to 45 show scanning electron microscope (SEM) images showing the cross-sectional shapes of the prepared porous separator films (ULTEMTM CRS 5001 parts only) of Examples 24-26.

The SEM image demonstrates that this process is versatile and the process conditions are very critical to controlling the separator microstructure. Although U.S. Patent Application No. 7,439,291 covers polymeric resins that are at least partially crystalline, the process conditions used in Examples 1 to 11 are similar to those disclosed in U.S. Patent Application 7,439,291, that is, they all use alcohol-based solidification baths. The forms of Examples 1-11 typically contain two separate regions, the upper region containing finger-like macropores (> 5 microns) (SEM images of Examples 1-11) (See Figs. 4-14), the lower region contains very fine sponge-like micropores (<1 micron) (high magnification scanning electron microscope (SEM) images of Examples 4-5, 7, 11 and 16-23, 26 to 37). Sponge-like micropores are typically preferred, and such a structure combines a continuous porous path through a separator film combined with rigidity. However, the macropores provide a very open pore structure, i. E. Very low resistance to ionic flow through the separator, which has the advantage of increasing the ionic conductivity. In fact, depending on the target performance of the separator film, an appropriate balance between these two can be pursued.

Examples 4, 6, 8 and 10 all used the same coagulation bath (22 ° C isopropanol), but the dope solution composition (solvent and polymer concentration) was different. Corresponding microscope images show that the pore structure has changed, and all of these separators have macropores. Similar conclusions are drawn in Examples 5, 7, 9 and 11, although the ratio of macropores varies significantly, but all of these separators also contain macropores. In the case of the LIPS process, higher polymer concentrations can generally delay phase separation kinetics and thus can be used to reduce the amount of macropores. Also, by comparing Examples 6, 7, 10, and 11 with Examples 4, 5, 8, and 9, it can be seen that the composition disclosed herein decreases the ratio of macropores when the polymer concentration in the dope solution is increased Respectively. However, even at polymer concentrations as high as 20 wt%, macropores are still present. Also, high polymer concentration reduces the micropore pore size, which results in a very dense pore structure (e. G., Example 7).

As discussed, since the presence of the macropores will affect the mechanical performance of the film, the macroporous separator may be desirable in certain applications. For example, the presence of a large void typically results in a very high overall porosity, which will result in a relatively low stiffness of the separator. Also, macropores can induce vulnerability to porous films. However, as presented above, the alcohol-based solidification bath could not produce a structure with substantially no macropores. Examples 10 to 16 used different solidifying baths from the same dope solution. Solidification baths are a very effective way to change the type of separator. The use of ethyl acetate (Example 12) or acetone (Example 13) as a coagulation bath did not result in a decrease in macro voids. The use of heptane (Example 14) as a coagulant bath did not result in a finger emulsion cavity, but produced isolated macropores. The use of NMP as a coagulation bath (Example 15) resulted in a very dense film with no noticeable porosity and therefore did not undergo further analysis.

Examples 16 to 23 used tetrahydrofuran (THF) as a base material for a coagulation bath. It can be seen from Figures 18-25 and 30-37 that a separator essentially free of large voids was successfully produced using THF as the substrate for the solidification bath. Example 17 using a low polymer concentration and a temperature of 40 占 폚 is the only sample exhibiting large voids. When comparing the microvoid structure in Figs. 18 to 25 and 30 to 37, the separator manufactured using THF as the coagulation bath solvent is very different from the separator of Examples 1 to 14. Low temperature coagulation baths (Examples 16, 18, 20, 22) have a structure of the more flaky type, whereas the coagulation baths of high temperature (Examples 17, 19, 21, 23) It seems to be importing. This has a significant effect on the interrelation between porosity and porosity.

The apparent porosity, ionic conductivity and mechanical stiffness of the produced separator were characterized according to the procedures described above, and the results are shown in Figures 38-40.

[Table BB]

Table BB summarizes the data and also indicates the number of MacMullins for these separators. MacMullin number based on the study of MacMullin and Muccini (RB MacMullin and GA Muccini, AIChE J., 2, 393, 1956) is N _M Is defined as a = C / C _0, where C is the conductivity of the porous medium saturated with electrolyte, C ₀ is the bulk conductivity of the same electrolyte. The advantage of explaining MacMullin channel separator conductivity is the fact that MacMullin water is quite independent of the electrolyte used. The bulk conductivity (C0) of the electrolyte was given as 8.5 ± 0.5 mS / cm.

The apparent porosity of all the separators ranges from 27% to 82%. In Examples 6 and 7 and Example 14, they exhibit very high stiffness but have low porosity (< 30%) and are ion-insulated because they are not connected from top to bottom (no or few through pores are present) . For example, in Examples 12 and 13, large amounts of macropores result in very high apparent porosity (> 75%), very high ionic conductivity (> 2.5 mS / cm) and very low MacMullin number (NM = 3) , But also somewhat lower stiffness (<400 psi at 2% offset).

The apparent porosity of the separator (Examples 16 to 23) produced using THF as the coagulating bath is in the range of 50 to 82%. The higher temperature of the coagulation bath led to higher porosity, resulting in higher ionic conductivity and lower MacMullin number, and also lower mechanical stiffness. With the exception of Example 17, Examples 16 to 23 using THF as the coagulation bath all resulted in a separator essentially free of macropores. It has been found that the separator performance associated with ionic conductivity, MacMullin number and stiffness can be controlled by varying the film preparation conditions.

As an example, it has high apparent porosity (64%), high stiffness (> 1000 psi) and excellent ionic conductivity (1.5 mS / cm) with very low MacMullin number of NM = 5 for example 20, Providing superior characterization profiles for separator applications in battery and supercapacitor systems.

As evidenced by the comparison of Examples 24, 25 and 26 with Examples 12, 13 and 20, the stress at the 2% offset of the separator composed of the ULTEM CRS 5001 porous film on the porous PE substrate was significantly improved, Example In each case 306, 341 and 1058 to 746, 783 and 1842 show an increase in stress at 2% offset. The presence of porous PE substrates results in an increase in the number of MacMullins from 3, 3, and 5 to 9, 6, and 12, respectively. These results indicate that a balance between stress and ionic conductivity at a 2% offset can be modified by casting ULTEMTM CRS 5001 film on top of a porous polyethylene substrate.

Table CC shows the contact angle of Example 20 with respect to time, as measured in the electrolyte solution. Even after a short contact time of 10 seconds, the contact angle is already 20 ° or less, which suggests almost immediate wetting of the separator by the electrolyte solution, which is very beneficial for battery cell operation as well as battery cell operation.

[Table CC]

The electrolyte contact angle of Example 20

Figure 41 shows the high temperature melt integrity (HTMI) of Example 1 (many macro voids) and 20 (no macropores) and PE substrate and ULTEM CRS 5001 / PE multilayer separator. The results show that a separator with no large voids is beneficial for HTMI performance. Table DD summarizes shrinkage temperature (2% strain) and strain temperature (5% strain) according to NASA / TM - 2010-216099 test method. These results indicate that the ULTEM ™ CRS 5001 separator achieves a strain temperature well in excess of 200 ° C., the HTMI requirement for advanced lithium ion battery separators with improved safety performance, and has a break temperature of 240 ° C. or higher. Conventional commercial polyolefin-based separators such as Celgard (TM) 2340, Celgard (TM) 2500 and Tonen V25CGD separators have a significantly poorer HTMI and typical deformation temperatures are below 160 ° C (Table I). This is also reflected by the low deformation temperature (134 ° C) and the low rupture temperature (149 ° C) of the PE substrate. The results indicate that the ULTEM ™ CRS 5001 / PE multilayer separator exhibits a fracture temperature in excess of 229 ° C. The strain temperature value indicates that the PE substrate strain predominates at lower ULTEMTM CRS 5001 thickness, resulting in a strain temperature of 140 캜 (Example 27). Similarly, the ULTEMTM CRS 5001 strain predominates over the higher ULTEMTM CRS 5001 thickness (casting gap thickness 50 or 75 microns, Examples 28 and 29), resulting in a strain temperature of 235 DEG C or higher. The shrink temperature of the ULTEM ™ CRS 5001 / PE multilayer separator is constant at 120-130 ° C, which is equivalent to the shrink temperature of the PE substrate. This suggests that the melting of the PE occurs at similar temperatures for the PE substrate and the ULTEM ™ CRS 5001 / PE multilayer separator, which results in a shutdown mechanism at the ULTEM ™ CRS 5001 / PE multilayer separator (which relies on PE melt and consequently pore closure ) Is present.

[Table DD]

The HTMI performance of Examples 1, 20, 27, 28, 29 and PE substrates

Figure 42 shows the discharge capacity retention rate of Example 20 as compared to a commercial separator (Celgard 2320). 1200 cycles have been completed using the ULTEM ™ CRS 5001 based separator, which indicates that the degradation rate is much slower than the commercial Celgard ™ 2320 separator, which means that the battery with the ULTEM ™ CRS 5001 separator will be replaced with a battery with a commercial polyolefin separator Which means that they have a significantly better life time compared to the others.

N-methylpyrrolidone (NMP )

In one embodiment, the temperature of the closed system (i.e., there is no direct contact between the solution and the air atmosphere) or an elevated temperature (e.g., 140 to 202 ° C, see FIG. 46) (E.g. polyetherimide based on para-phenylenediamine) and then cast at reduced temperature (30-140 DEG C) to form a solid in a bath of water or other material The separator can be manufactured. By way of example, membranes for environments such as battery cells and / or capacitor cells, electrolytic energy storage devices, dialysis membranes, water filtration membranes, desalination membranes, gas separation membranes, etc. may be fabricated using the materials and processes described herein.

The following examples are presented to provide those of ordinary skill in the art with a complete disclosure and description of the manner in which the compounds, compositions, articles, apparatus and / or methods claimed herein are made and evaluated, and are provided by way of illustration only, There is no intention to restrict. While efforts have been made to ensure accuracy with respect to numbers (eg, quantity, temperature, etc.), some errors and deviations should be considered. Unless otherwise indicated, parts are parts by weight, temperatures are in degrees Celsius or ambient temperature, pressures are atmospheric or atmospheric pressure approximations, and the coagulation solvent is in the liquid phase.

material

In one embodiment, a plurality of materials may be used in the preparation of the water-soluble polymeric film described herein and illustrated below.

Example

As shown and disclosed herein, polyetherimides (PEI) based on para-phenylenediamines (ULTEM (TM) CRS 5000 series of SABIC) are excellent materials for solvent-resistant membranes. By way of example, membranes for environments such as battery cells and / or capacitor cells, electrolytic energy storage devices, dialysis membranes, water filtration membranes, desalination membranes, gas separation membranes, etc. may be fabricated using the materials and processes described herein.

In one embodiment, the chemical resistant ULTEM (TM) CRS 5000 grade is generally considered to be insoluble in common solvents (see U.S. Patent No. 7,439,291), and a solvent having a health ranking of 2 or less on NFPA Fire Diamond (LIPS) or a vapor-induced phase separation (VIPS) approach to maintain a stable solution at low or room temperature to produce a porous membrane. Surprisingly, however, we have found that N-methylpyrrolidone (NMP) can dissolve the chemical resistant ULTEM ™ grade (eg, ULTEM ™ CRS 5000 series of SABIC) at elevated temperatures and is summarized in Tables AAA and BBB And found it useful for casting battery separators at room temperature or near room temperature. NMP allows the use of coagulation baths that contain water to be fully miscible with water, having a health ranking of 2 or less on NFPA Fire Diamond (i.e., reduced toxicity relative to most phenol and cresol-based solvents) It is a beneficial solvent for the casting of battery separators.

[Table AAA]

Solubility of ULTEM ™ CRS 5011K in common solvents

[Table BBB]

Solubility of ULTEM ™ CRS 5011K in phenol and cresol-based solvents (health ranking of 3 or more on NFPA fire diamond)

In one embodiment, N-methyl-2-pyrrolidone (NMP) is added to the solvent-resistant poly (NMP) in an open system (i.e., direct contact between solution and air atmosphere) at elevated temperature The chemical resistant porous film can be prepared by dissolving the etherimide and then casting at a reduced temperature (30-140 DEG C) and solidifying in a water bath. In Fig. 46, the dissolution temperature was determined by visual observation that the polymer dissolved in the solvent and the solution completely changed in transparency. Figure 47 shows the separation temperature as a function of concentration, as a function of concentration, in the rectified state, which was measured by determining the temperature at which the solution showed a sudden significant increase in viscosity upon cooling from 170 ° C, which is an indication of gelation ).

In one embodiment, the dissolution temperature is a critical parameter when dissolving the chemical resistant ULTEM (TM) CRS 5000 grade in NMP. In an open system, dissolution of 12 wt% ULTEM ™ CRS 5001K in NMP can be achieved within 12 minutes at an average temperature of 200 ° C, but takes 28 minutes at an average temperature of 190 ° C. In addition, the dissolution time depends on the physical form of the ULTEM (TM) CRS 5001K (e.g., pellet to powder) and agitation mechanism.

In one embodiment, unexpected results were obtained when the ULTEMTM CRS 5000 was heated in an NMP mixture in an open system (i.e., the solvent was in contact with an air atmosphere at atmospheric pressure conditions), as described in Table CCC below, The solution is completely dissolved and the solution is stable at room temperature for up to 2 hours (depending on the composition) (i.e. no phase separation takes place).

[Table CCC]

A more detailed solubility assay demonstrated the effect of ULTEMTM CRS 5001K concentration on solution stability at room temperature (Table DDD). The solution was dissolved at high temperature in an open system and cooled in a closed system using a water bath. These results show that 15 wt% ULTEM ™ CRS 5001K / NMP is still transparent at room temperature for several minutes.

[Table DDD]

In one embodiment, cooling these solutions of the solvent-soluble polyetherimide in hot NMP in a water bath at room temperature compared to cooling the same solution in a 50 ° C water bath or through contact with air at room temperature A significant difference is observed. As an example, the ULTEM (TM) CRS 5000 resin is separated at relatively high temperatures when cooled very slowly, i.e. the phase separation is close to the rectified state (as shown in FIG. 47). As a further example, the solution is stable at room temperature (i. E., No phase separation) for a significant period of time (depending on the composition) as described in Table DDD.

In one embodiment, the solution may be prepared by boiling the NMP solution for a period of time (e.g., 3-5 minutes) while the resin is placed in the NMP and shaking or stirring is continued. Moisture analysis of NMP using a Karl Fischer titration apparatus shows a drastic reduction in moisture content in an open system, which is explained by the fact that NMP and water do not form an azeotropic mixture (see Raginskaya LM: N-methyl -2-Pyrrolidon-Wasser, Prom. Sint Kaucuka (1975) 1-3), and therefore water mostly evaporates from boiling NMP. No significant changes in the molecular weight of ULTEM ™ during the dissolution process were observed. GPC analysis on ULTEM ™ CRS 5000 before and after the dissolution process confirmed that the molecular weight remained constant, ie polymer degradation or other polymer chain modifications did not occur.

In one embodiment, 10 wt% of a solvent-soluble polyetherimide (e.g. ULTEMTM CRS 5001K) is dissolved in N-methyl-2-pyrrolidone (NMP) at 200 &lt; 0 &gt; C in an open system, And then solidifying in a water bath, a chemical resistant porous film can be produced. N-methyl-2-pyrrolidone (NMP) has a health ranking of only 2 on NFPA Fire Diamond (according to the US Centers for Disease Control and Prevention - http://www.cdc.gov) Are considered to be much more environmentally friendly as compared to cresol solvent systems. In addition, the NMP is completely miscible with water, and since the water is a poor solvent for the polyetherimide, the coagulation bath used in the phase inversion process may be based on water, optionally in combination with NMP or other solvents.

In one embodiment, 10 wt% of a solvent-soluble polyetherimide (e.g., ULTEM ™ CRS 5001K) and 10 wt% of inorganic particles are dissolved in N-methyl-2-pyrrolidone (NMP) Followed by casting at room temperature and solidification in a water bath, whereby a chemical resistant porous film can be produced.

In one embodiment, 12 wt% of a solvent-soluble polyetherimide (e.g., ULTEMTM CRS 5001K) is dissolved in N-methyl-2-pyrrolidone (NMP) at 200 &lt; 0 &gt; C in an open system, The chemical resistant porous film can be produced by casting the film on the top of the film at room temperature and solidifying in a water bath.

Example 30 - Membrane casting conditions

48A shows a typical shape obtained by casting according to Example 30. Fig. 48B is an enlarged view of a typical shape obtained by casting according to the embodiment 30. Fig.

Example 31 - Membrane casting conditions

49A shows a typical shape obtained by casting according to Example 31. Fig. 49B is an enlarged view of a typical shape obtained by casting according to Example 31. Fig.

Example 32 - Membrane casting conditions

50A shows a typical shape obtained by casting according to Example 32. Fig. 50B is an enlarged view of a typical shape obtained by casting according to Example 32. Fig.

Example 33 - Membrane casting conditions

51A shows a typical form obtained by casting according to Example 33. Fig. 51B is an enlarged view of a typical shape obtained by casting according to Example 33. Fig.

Example 34 - Membrane casting conditions

52A shows a bottom surface of a typical shape obtained by casting according to Example 34. Fig. 52B shows a cross section of a typical shape obtained by casting according to Example 34. Fig.

Example 35 - Membrane casting conditions

53A shows a bottom surface of a typical shape obtained by casting according to Example 35. Fig. 53B shows a cross section of a typical shape obtained by casting according to Example 35. Fig.

Example 36 - Membrane casting conditions

54 shows a cross section of a typical shape obtained by casting according to Example 36. Fig.

Example 37 - Membrane casting conditions

55 shows a cross section of a typical shape obtained by casting according to Example 37. Fig.

Example 38 - Membrane casting conditions

56 shows a typical form obtained by casting according to Example 38. Fig.

Example 39 - Membrane casting conditions

57 shows a typical form obtained by casting according to Example 39. Fig.

Example 40 - Membrane casting conditions

58 shows a typical form obtained by casting according to Example 40. Fig.

Example 42 - Membrane casting conditions

60 shows a typical form obtained by casting according to Example 42. Fig.

Example 43 - Membrane casting conditions

61 shows a typical form obtained by casting according to Example 43. Fig.

Example 44 - Membrane casting conditions

62 shows a typical form obtained by casting according to Example 44. Fig.

Example 45 - Membrane casting conditions

63 shows a cross section of a typical shape obtained by casting according to Example 45. Fig.

Example 46 - Membrane casting conditions

Fig. 64 shows a cross section of a typical shape obtained by casting according to Example 46. Fig.

Determination of air permeability (Gurley Densometer, JIPS 8117 (2009) - Determination of air osmosis and air resistance (medium size) - Gurley method) for various water / NMP liquid mixtures as well as for ULTEM ™ CRS 5011K separators solidified in water vapor Respectively. The air permeability is measured in Gurley seconds and is generally directly related to the ionic conductivity of the separator in an electrochemical cell environment. The high Gurley value suggests low air transport through the membrane, which is typically understood as a low ionic conductivity. As an example, the measured ULTEMTM CRS 5011K separator prepared using a liquid water / NMP coagulation bath exhibited a Gurley number in the range of 12 to 544 seconds, indicating that the ionic conductivity of the membrane can vary widely depending on the casting conditions It suggests. Similarly, the ULTEM CRS 5001K separator manufactured using steam coagulation exhibited a Gurley number of 38 seconds. These results show that these new materials are similar or better than commercial polyolefin separators such as Celgard ^® 2320, 2400, 2340 and 2500 with Gurley numbers of 586, 620, 846, 217, 191 and 293 respectively, as well as Tonen V25CGD and V25EKD, Indicating that it has a number.

[Table DDD]

Air permeability (Gurley) value of ULTEM ™ CRS 5011K separator manufactured under various conditions

Some embodiments of the systems and methods disclosed herein are set forth below.

Example 1: Anode; Cathode; A system comprising a separator disposed between an anode and a cathode, wherein the separator is formed from a thermoplastic polymer having a glass transition temperature of 180 DEG C or higher, the electrolyte solution is disposed adjacent to the separator, the thermoplastic polymer is not significantly soluble in the electrolyte solution , The thermoplastic polymer having an electrolyte contact angle of 30 DEG or less.

Embodiment 2: The system of embodiment 1, wherein the electrolyte comprises 0 wt% to 50 wt% ethyl carbonate, based on the weight of the total solvent composition; 0 wt% to 80 wt% dimethyl carbonate, based on the weight of the total solvent composition; And from 0 wt% to 80 wt% ethyl methyl carbonate based on the weight of the total solvent composition.

Embodiment 3: As a system according to any one of Embodiments 1 to 2, the electrolyte comprises more than 0 wt% to 50 wt% of ethyl carbonate based on the weight of the total solvent composition; From greater than 0 wt% to 80 wt% of dimethyl carbonate, based on the weight of the total solvent composition; And from 0 wt% to 80 wt% ethyl methyl carbonate based on the weight of the total solvent composition.

Embodiment 4: As a system according to any of Embodiments 1 to 3, wherein the separator has an electrolyte contact angle of 20 DEG or less.

Embodiment 5: A system as in any of Embodiments 1 to 4, wherein the separator has a deformation temperature exceeding 180 캜.

Specific Example 6: As a system of any of Embodiments 1 to 5, the separator was made of 1,3-diaminobenzene, 1,4-diaminobenzene, 4,4'-diaminodiphenylsulfone, oxydianiline, 1,3 (PEI) comprising structural units derived from at least one diamine selected from the group consisting of bis (4-aminophenoxy) benzene or combinations thereof.

Embodiment 7: As a system according to any one of Embodiments 1 to 6, the thermoplastic polymer has an electrolyte contact angle of less than 30 degrees.

8. The system of any one of embodiments 1 to 7, wherein the contact angle is 25 DEG or less.

Aspect 9: A system according to any one of embodiments 1 to 8, wherein the contact angle is 20 DEG or less.

Embodiment 10: Providing an injectable polymer solution comprising a thermoplastic polymer in a solvent, wherein the polymer is chemically resistant to the electrolyte solution and the polymer has a normalized dry weight of at least 90%; And forming a porous film from the polymer solution.

Embodiment 11: The method of Embodiment 10, wherein the chemical resistant polymer has a weight concentration in a solvent of 5% to 30% by volume.

Embodiment 12: As a method according to any of Embodiments 10 to 11, the polymer includes a polyetherimide, a polyketone, a polyester, poly (4-methylpentene), polyphenylene ether or polyphenylene sulfide, How to.

Embodiment 13: As a method according to any of Embodiments 10 to 12, the solvent is at least one selected from the group consisting of a phenol-based solvent, 4-chloro-3-methyl-phenol, 4-chloro- Phenol, 2,4-dichloro-phenol, 2,6-dichloro-phenol, 4-chloro-phenol, 2-chloro-phenol, o- Xylenol, 2,6-xylenol, or resorcinol, or a combination thereof.

Embodiment 14: Providing an injectable polymer solution comprising a polymer in a solvent, wherein the polymer is chemically resistant to the electrolyte solution, the polymer has a normalized dry weight of at least 90%, and the solvent is 2 &lt; RTI ID = 0.0 &gt; Having the following health rankings; And forming a film from the polymer solution.

The method of embodiment 14 wherein the solvent is selected from the group consisting of 2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1-cyclohexyl-2-pyrrolidone, 1- (2- Pyrrolidone, 1-octyl-2-pyrrolidone, 1-N-ethoxycarbonyl-3-pyrrolidone, N- Lt; RTI ID = 0.0 &gt; of: &lt; / RTI &gt; a pyrrolidone-based solvent.

The method of any one of embodiments 14-15, wherein the step of providing an injectable polymer solution comprises contacting the polyphenylene (NMP) in N-methylpyrrolidone (NMP) at elevated temperature in one of the open system or the closed system. &Lt; / RTI &gt; ether or polyetherimide.

Embodiment 17: A method according to any of Embodiments 14 to 16, wherein the polymer comprises polyetherimide or polyphenylene ether, or a combination thereof.

Example 18: As a method of any of Embodiments 14 to 17, the polymer may be 1,3-diaminobenzene, 1,4-diaminobenzene, 4,4'-diaminodiphenylsulfone, oxydianiline, 1,3 -Bis (4-aminophenoxy) benzene, or a combination thereof. &Lt; RTI ID = 0.0 &gt; 5. &lt; / RTI &gt;

Embodiment 19: A method according to any of Embodiments 14 to 18, wherein the polymer solution comprises inorganic particles.

Embodiment 20: As a method according to any one of Embodiments 14 to 16, the step of forming a film from a polymer solution includes casting a wet thin film from a polymer solution; And immersing the wet-molded polymer solution in a coagulation bath comprising a non-solvent for the polymer to provide a coagulated polymer film, and then removing the solvent from the coagulated polymer film; Or exposing the polymer solution wet-molded to the vapor of the non-solvent for the polymer and then removing the solvent from the coagulated polymer film.

The method of embodiment 20 wherein the non-solvent is selected from the group consisting of water, a pyrrolidone-based solvent, a phenolic-based solvent, acetone, methanol, ethanol, butanol, isopropanol, tetrahydrofuran, dichloromethane, ethyl A solvent such as methanol, ethanol, propanol, isopropanol, butanol, isopropanol, isopropanol, butanol, isopropanol, butanol, isobutanol and the like, acetate, methyl acetate, toluene, hexane, cyclohexane, pentane, cyclopentane, benzene, Benzene, xylene, hexafluoroisopropanol, dichloromethane, tetrafluoroacetate, tetrachloroethane, 1,3-dimethyl-2-imidazolidinone, or combinations thereof.

[0215] Embodiment 22: The method according to any of Embodiments 10-21, wherein the normalized dry weight is 93% to 101%.

[0216] Embodiment 23: As a method according to any of Embodiments 10 to 22, the normalized dry weight is 96% to 101%.

Embodiment 24: The method of any of embodiments 10-23, wherein the normalized dry weight is 98% to 101%.

Embodiment 26: As a method according to any of Embodiments 10 to 13, wherein the film has no macropores.

Embodiment 26: A method according to any one of Embodiments 14 to 24, wherein the film and the film have no macropores.

Embodiment 27: A method of forming a structure, comprising: forming a multi-layer structure in which the porous film according to any one of Embodiments 10 to 13 is a multi-layered substrate.

Embodiment 28: A method for forming a structure, comprising: forming a multi-layer structure in which the porous film according to any one of Embodiments 10 to 26 is a multi-layered substrate.

While methods and systems have been described in connection with preferred embodiments and specific embodiments, the scope thereof is not limited to the specific embodiments shown, and the embodiments herein are intended to be illustrative, not limiting in all respects.

Unless expressly stated otherwise, it is in no way interpreted that any method presented herein should perform its steps in any particular order. Thus, unless the method claim does not actually cite the order in which it follows, or if the claim or the description does not specifically state that the steps are to be limited to a particular order, it is not in any way sequenced in any way Do not. This is a matter of logic in relation to the arrangement of steps or workflow; A simple meaning derived from a grammatical structure or punctuation; But retains any possible circumstantial basis for interpretation, including the number or type of embodiments described herein.

Various publications are referred to throughout this specification. The disclosures of these publications are incorporated herein by reference in their entirety to more fully describe the state of the art to which the present methods and systems belong.

It will be apparent to those skilled in the art that various modifications and variations can be made without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification and practice herein disclosed. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit being claimed by the following claims.

Claims (18)

A system, comprising:
Anode;
Cathode;
A separator disposed between the anode and the cathode; And
And an electrolyte solution disposed adjacent to the separator,
Wherein the separator is formed from a thermoplastic polymer having a glass transition temperature of 180 DEG C or higher and the thermoplastic polymer is not significantly soluble in the electrolyte solution and the thermoplastic polymer has an electrolyte contact angle of 30 DEG or less.
The electrolyte of claim 1, wherein the electrolyte comprises 0 wt% to 50 wt% ethyl carbonate, based on the weight of the total solvent composition; 0 wt% to 80 wt% dimethyl carbonate, based on the weight of the total solvent composition; And from 0 wt% to 80 wt% ethyl methyl carbonate based on the weight of the total solvent composition.
3. The system according to claim 1 or 2, wherein the separator has an electrolyte contact angle of 20 DEG or less.
4. The system according to any one of claims 1 to 3, wherein the separator has a deformation temperature in excess of &lt; RTI ID = 0.0 &gt; 180 C. &lt; / RTI &gt;
The positive electrode of claim 1, wherein the separator is selected from the group consisting of 1,3-diaminobenzene, 1,4-diaminobenzene, 4,4'-diaminodiphenylsulfone, oxydianiline, (PEI) comprising a structural unit derived from at least one diamine selected from 3-bis (4-aminophenoxy) benzene or a combination thereof.
Providing an injectable polymer solution comprising a thermoplastic polymer in a solvent, wherein the polymer is chemically resistant to an electrolyte solution, the polymer having a normalized dry weight of at least 90%; And
And forming a porous film from the polymer solution.
7. The method of claim 6, wherein the chemical resistant polymer has a weight concentration in the solvent of between 5% and 30% by volume.
The method according to claim 6 or 7, characterized in that the polymer comprises polyetherimide, polyketone, polyester, poly (4-methylpentene), polyphenylene ether or polyphenylene sulfide, or a combination thereof Lt; / RTI &gt;
9. A process according to any one of claims 6 to 8, wherein the solvent is selected from the group consisting of phenolic solvents, 4-chloro-3-methyl-phenol, 4-chloro- Phenol, 2-chloro-phenol, o-cresol, m-cresol, p-cresol, 4-methoxy-phenol, Catechol, benzoquinone, 2,3-xylenol, 2,6-xylenol or resorcinol, or combinations thereof.
Providing an injectable polymer solution comprising a polymer in a solvent, wherein the polymer is chemically resistant to an electrolyte solution, the polymer having a normalized dry weight of at least 90%, and the solvent is not more than 2 on NFPA Fire Diamond Having a health ranking of; And
And forming a film from the polymer solution.
11. The method of claim 10, wherein the solvent is selected from the group consisting of 2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1-cyclohexyl-2-pyrrolidone, 1- (2-hydroxyethyl) Pyrrolidone, 1-octyl-2-pyrrolidone, 1-N-ethoxycarbonyl-3-pyrrolidone, N-methyl- &Lt; / RTI &gt; wherein the solvent comprises a pyrrolidone-based solvent.
12. The method of claim 10 or 11, wherein providing the injectable polymer solution comprises contacting the injectable polymer solution with polyphenylene ether or poly (phenylene ether) in N-methyl pyrrolidone (NMP) at elevated temperature in one of the open system or the closed system. &Lt; / RTI &gt; dissolving the ether imide.
13. The method according to any one of claims 6 to 12, wherein the polymer comprises polyetherimide or polyphenylene ether, or a combination thereof.
14. The polymer according to any one of claims 6 to 13, wherein the polymer is selected from the group consisting of 1,3-diaminobenzene, 1,4-diaminobenzene, 4,4'-diaminodiphenylsulfone, oxydianiline, A polyetherimide comprising a structural unit derived from at least one diamine selected from 3-bis (4-aminophenoxy) benzene or a combination thereof. 15. The method according to any one of claims 6 to 14, wherein the polymer solution comprises inorganic particles.
16. A method according to any one of claims 6 to 15, wherein the step of forming a film from the polymer solution comprises: casting a thin film wet from the polymer solution; And
Immersing the wet-molded polymer solution in a coagulation bath comprising a non-solvent for the polymer to provide a coagulated polymer film, and then removing the solvent from the coagulated polymer film; Or exposing the wet-molded polymer solution to a vapor of a non-solvent for the polymer and subsequently removing the solvent from the coagulated polymer film.
The method of claim 16, wherein the non-solvent is selected from the group consisting of water, pyrrolidone-based solvents, phenolic-based solvents, acetone, methanol, ethanol, butanol, isopropanol, tetrahydrofuran, dichloromethane, ethyl acetate, , Hexane, cyclohexane, pentane, cyclopentane, benzene, chloroform, diethyl ether, dimethylacetate, ethylene dichloride, dimethylsulfoxide, acetonitrile, propylene carbonate, anisole, 1,2-dichlorobenzene, xylene, hexa Fluoroethane, fluoro isopropanol, dichloromethane, tetrafluoroacetate, tetrachloroethane, 1,3-dimethyl-2-imidazolidinone, or combinations thereof.
A method of forming a structure, comprising: forming a multi-layer structure in which the porous film of any one of claims 6 to 9 is a multi-layered substrate.

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