TW201232893A - Multi-layer article of polyimide nanoweb with amidized surface - Google Patents

Abstract

The present invention is directed to the preparation and use of aromatic polyimide nanowebs with amide-modified surfaces. Uses include as a filtration medium, and as a separator in batteries, particularly lithium-ion batteries. The invention is also directed to a method comprising the aromatic polyimide nanoweb with amide-modified surface. The invention is further directed to a multi-layer article comprising the aromatic polyimide nanoweb with amide-modified surface, and to an electrochemical cell comprising the multi-layer article.

Description

201232893 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to the preparation and use of an aromatic polyimide nanoweb having a modified surface of a guanamine. Uses include as a filter medium and as a separator in a battery, especially an ion battery. The invention also relates to a filtration apparatus comprising an aromatic polyamidene nanonet having a guanamine-modified surface. The invention further relates to a multilayer article comprising an aromatic polyamidene nanoweb having a guanamine-modified surface and to an electrochemical cell comprising the multilayer article. [Prior Art] Polyimine is of great value in the market due to its strength, chemical inertness and thermal stability in various environments. In the past few years, 'electrospun or electroblown non-woven nano-networks have been made from poly-imine, and for the first time, the properties of poly-imine and the high porosity are required. Type structure. The use of a wholly aromatic polyamidene nanowire as a separator in Li-ion batteries and other electro-chemical cells is disclosed in co-pending applications 61/286,618, 61/286,628 and 61/286,623.

Honda et al., JP-A-2004-308031A, discloses a process for the preparation of a polyamidene nanowire which is prepared by electrospun polyplyamic acid solution followed by oxime imidization. Thousands of polyimine compositions have been disclosed as including aromatic polyimine. The application as a battery separator has been disclosed. 4 201232893

Jo et al., WO2008/018656, discloses the use of a non-all aromatic polyamidene network as a battery separator in Li and Li ion batteries.

European Patent 0 401 00 581 to Hayes discloses the grafting of hydrocarbons onto the surface of a semipermeable, permselective polyimine film. Polyethylenimine is known to be susceptible to hydrolysis at temperatures above 1 〇 (TC is susceptible to hydrolysis. It is also known to adhere polyimine films to certain substrates (such as epoxy resins). Specially formulated adhesives are used. For all end uses, the surface chemistry of modified aromatic polyamidene mesh is modified to improve compatibility, increase or decrease wettability, and protect surfaces from Chemical etching while preserving the porosity of the nano mesh structure. [Invention] In one aspect, the present invention provides an article comprising a nano network of aromatic polyimide nanofibers (nan0fiber). The nanoweb has a free surface region, at least a portion of which comprises a primary phthalamide (SeC〇ndary amide), the secondary guanamine comprising a functional group containing a hydrocarbon radical. Wherein the functional group further comprises a functional group containing oxygen, nitrogen or sulfur. In a further embodiment, the functional group containing oxygen, nitrogen or sulfur is an amine group. In another aspect, The invention provides a chemical for changing an aromatic A method for the surface of a ruthenium amide network, the method comprising: contacting a primary amine of a sulphide tanning nanocapsule with a primary amine of 201232893 liquid contact temperature in the range of room temperature to 150 ° C, contact The period is in the range of 1 to 240 minutes, wherein the primary amine comprises a functional group containing a ketone radical. In one embodiment, the functional group further comprises a functional group containing oxygen, nitrogen or sulfur. In an embodiment, the oxygen, nitrogen or sulfur containing functional group is an amine group. In another aspect, the invention provides a method for filtering 'the method comprising: mixing a solid with a fluid Wetly colliding with the surface of a surface-modified polyimine mesh, and one of the mixture is enriched with a fluid portion transported through the surface-modified polyamidene network' and one of the mixtures The solid-rich portion is not transported through, and wherein the surface-modified polyimine mesh comprises a nanoweb containing aromatic polyamidene nanofibers having a free surface region At least one of the free surface areas The first-stage guanamine comprises a functional group containing a hydrocarbon-based radical. In one embodiment, the functional group further comprises an oxygen-containing, nitrogen-, functional group. In a further embodiment, the oxygen-containing, nitrogen-containing Or the sulfur g month t* group is an amine group. In another aspect, the present invention provides a filtering device comprising: a housing, the housing is provided with a first opening to introduce a dummy; ::=, and a second port to discharge a filtered fluid, the surface of the shell is modified with an aromatic polyamidene network, the nano-network: 'sigh so that the mixture to be filtered can be Wetly colliding with the nano, 3 t to make the fluid-rich portion of the mixture pass: this: the poly-imine mesh, and the mixture - rich in solids - passes through, And wherein the surface modified polyamic acid imide: 6 201232893 The first mesh of the polyamidene nanofiber, the nano mesh has a free surface area, and at least a portion of the free surface area %-grade guanamine, which contains a functional group containing a hydrocarbon radical. In one embodiment, the functional group further comprises a functional group containing oxygen, nitrogen or sulfur. In a further embodiment, the oxygen, nitrogen or sulfur-containing lyophilized >=* group is an amine group. In another aspect, the present invention provides a multilayer article comprising a -electrode material, a second electrode material, and a porous separator disposed between and in contact with the first and second electrode materials Wherein the "Hylon porous separator" comprises a nanoweb containing aromatic polyamidene nanofibers, the nanoweb having a free surface region, the portion of the free surface region comprising a primary amine The secondary guanamine contains a functional group containing a hydrocarbon radical. In an embodiment, the functional group further comprises a functional group containing oxygen, gas or sulfur. In the -in-step, the functional group containing oxygen, nitrogen or sulfur is an amino group. In another aspect, the present invention provides an electrochemical cell comprising a housing disposed therein, an electrolyte, and a plurality of articles at least partially immersed in the electrolyte, the multilayer article comprising - a first metal current collector, a first electrode material electrically conductively contacting the first metal current collector, a second electrode material in conductive contact with the first material, and a first electrode material disposed on the first electrode a porous separator in which the material is in contact with the second electrode material; and a second metal current collector in electrical contact with the second electrode material, wherein the porous separator comprises - an aromatic polyfluorene The nanoweb of 201238893 has a free surface region, at least a portion of which contains a first-order guanamine. The secondary guanamine contains a functional group containing a hydrocarbon radical. . In one embodiment, the functional group further comprises a functional group containing oxygen, nitrogen or sulfur. In a further embodiment, the oxygen, nitrogen or sulfur-containing sulphate b group is an amine group. [Embodiment] The present invention provides a surface-modified aromatic polyamidene nanonet having various characteristics characterized by a change in surface tension, novel chemical functionality, and resistance to chemical deterioration. The surface modified aromatic polyamidene nanowire can be used as a filter medium and as a separator in a battery, particularly a lithium ion battery. For the purposes of the present invention, the term "nonw〇ven" shall be defined in accordance with ISO 9092: "A sheet, mesh or batt that is manufactured and has a directional arrangement or a disorderly arrangement of fibers, which is frictionally / or = combination of strength and / or adhesion, exclude paper and woven, knitted, velvet, stitched binding yarn or silk or wet felting products, whether or not there is extra Sewing." Fibers can be natural or artificial sources. They may be cotton fibers or continuous filaments or formed in situ. The term "m" when referring to this document, represents a subset of the non-articles, where the fiber system is designated "nanofiber" and is characterized by a cross-sectional diameter that is less than! Micron. The nanoweb used herein, a relatively flat, flexible and porous planar structure, is formed by laying a plurality of continuous filaments. < 201232893 The term "nanofiber" as used herein means an average number of straight positions less than 1000 nm, even less than nm, even between about 5 and 500 nm and even between about 100 nm and 400 nm. The fiber between. In the case of non-circular cross-section nanofibers, the term "diameter" as used herein refers to the largest cross-sectional dimension. The rice fiber used in the present invention is mainly composed of one or more wholly aromatic polyimine. For example, the present invention employs more than 8 J) by weight of more than 8 J) by weight—or a plurality of wholly aromatic polyimines, more than 9% by weight of one or more wholly aromatic polyimines, more than 100% by weight. Knife ratio of one or more wholly aromatic polyimine, more than one weight percent of one or more wholly aromatic polyimine, more than 99 9 weight percent - or more wholly aromatic polyimine or just percentage by weight - or a variety of wholly aromatic polyimines are prepared. It is made by a method of grouping: an electric blowing (PA A ) solution, followed by a slanting ridge. The nano net used in the present invention can be selected from the group consisting of the following

Never suffocate the sulphur sputum." Formed by a poly-polyamine, the polyamine 201232893 aminic acid is characterized by having at least one aromatic group in its polymer backbone repeat unit. A suitable PAA is prepared by polycondensation of at least one carboxylic acid dianhydride with at least one diamine, at least one of which is aromatic. In one embodiment, the aromatic polyimine is a wholly aromatic polyimine. The phrase "all-aromatic polyamidene network" refers to a nanoweb formed by hydrazide-PAA nanoweb, which is obtained by polycondensation of at least one aromatic carboxylic dianhydride and at least one Prepared from an aromatic diamine. In one embodiment, a fully aromatic polyamidene nanoweb suitable for use herein comprises at least 90% aminated iminated chitosan, and wherein at least 95% of the polymer backbones are adjacent The bond between the benzene rings is achieved by a covalent bond or an ether bond. Up to 25%, preferably up to 20%, and most preferably up to 1% by weight of the bond may be achieved by aliphatic carbon, sulfide, ε wind, ph〇sphide or phosphine functionality or a combination thereof . The aromatic ring constituting the polymer backbone of up to 5 Å/Å may have a ring substituent of an aliphatic carbon, a sulfide, a sulfone, a phosphide or a phosphine. 90% quinone imidization means that 90% of the proline precursor of the polyproline precursor has been converted to quinone. Preferably, the wholly aromatic polyimine does not contain an aliphatic carbon, sulfide, sulfone, phosphide or phosphine. Suitable aromatic dianhydrides include, but are not limited to, pyromellitic dianhydride (PMDA), biphenyltetracarboxylic dianhydride (BPDA), and mixtures thereof. Suitable aromatic diamines include, but are not limited to, diaminodiphenyl ether (0DA), 1,3-bis(4-aminophenoxy)benzene (R0DA), and mixtures thereof. Preferred dianhydrides include pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, and mixtures thereof. Preferred diamines include diaminodiphenyl ether, 1,3-bis(4-aminophenoxy)benzene, and mixtures thereof. The best are PMDA and 〇DA. Suitable wholly aromatic polyimines are described by the following structural formula 10 201232893 Ο Ο

II II --, Α ( —Ατ·- —

V V

II II ο ο L Jn wherein 500, preferably 21000, Ar and Ar are each independently formed as a group of a compound of the formula, and the oxime aromatic compound includes, but not limited to, benzene, naphthalene, biphenyl, diphenylamine, Diphenyl ketone, diphenylenyl (wherein the dilute contains 1-3 carbons), diphenylsulfonone, diphenylsulfide, diphenylphosphone, phosphorus diphenyl Diphenylphosphate, bismuth bite,

Wherein R1, R2 and R3 are independently an alkenyl radical having 1-3 carbons. In one embodiment, the polyamidene nanoweb consists essentially of polyamidene nanofibers formed from pyromellitic dianhydride (PMDA) and oxydiphenylamine (ODA) having the following Structure representative, repeat, single 201232893

Polyimine-like refers to the name that forms the repeating gas. This article will continue this mode of operation. The =amine ‘ refers to the polyfluorene a ... PMDA/ODA composed of repeating units of the table. Long Yan #人 Although the invention of this article is not limited to this, a method can affect the chemical choice of an aromatic polyamidene network. Over = one liver will result in a polyglycol with amine-bearing end groups with chemically active hydrogen being stoichiometrically adjusted to give a slight excess of dianhydride, or by: de:: such as phthalic anhydride) The amines are used to prepare the polylysine in solution, and the glutamic acid/DMAA methyl acetamide (DMAC) or dimethylformamide is used in the practice of the present invention. 'The system is formed by electroblowing the polyamine liquid, which is described in the literature of Kim et al., and is described later in Tanaka. In another method suitable for use in the practice of the invention, the I-electrolytic solution of the polyaminic acid solution is formed to form a nanoweb, as described in ^uang et al'' Adv. Mat. DOI: 10.1002/adma.200501806. The wholly aromatic polyamidene used in the present invention is highly insoluble. The person skilled in the art must first form a nanoweb from polylysine and then iodize the resulting nanoweb. For the simple formation of the polyamidite network formed by imidization, the nanoweb may be first subjected to solvent extraction in a vacuum oven with nitrogen purge at a temperature of about 100 ° C; after extraction, followed by extraction The nanoweb is heated to a temperature of 201232893 300 to 350 C for about 10 minutes or less, preferably 5 minutes or less, to completely iridize the nanoweb. H-imidization according to the method of the present invention achieves at least a general, preferably ruthenium imidization. In most cases, the analytical method showed that 醯 imidization was less than 100%, even for long-term 醯 醯 imidization. For the purpose of use only, when the slope of the curve of the yttrium imidation versus time is zero, it is considered to achieve thorough imidization. The aromatic polyamidene nanoweb suitable for use in the practice of the invention may be a so-called enhanced nanoweb characterized by a crystallinity index of at least 0.2. In one embodiment, the enhanced nanoweb consists essentially of a crystallinity index, at least G.2 of PMDa/qDA, fiber. An enhanced aromatic polyamidene nanonet is characterized by higher strength, lower electrolyte solvent absorption, and reduced physical property loss caused by electrolyte solvent compared to the corresponding unreinforced aromatic polyugly imidate network. It is believed that the enhancement of the properties observed in the enhanced aromatic polyamidene nanonet is due, at least in part, to an increase in crystallinity which is developed in the process of preparing an enhanced nanoweb.

The enhanced aromatic polyamidene nanowires suitable for use in the present invention are prepared by heating an aromatic polyamidene nanoweb in an annealing range. Annealing fe is highly correlated with the composition of the material. For pMDA/〇DA, the annealing range is 400 to 500 °C. For BPDA/RODA, it is about 2003⁄4; if heated to 4〇〇t, BpDA/R〇DA will decompose. In general, in the process of the present invention, the temperature at which the annealing range begins is at least 5 Torr at the temperature at which it is made. Hey. For the purpose of the present invention, the specific imidization temperature of a specific aromatic polyamidonet network is lower than 500 ° C, and the heating rate is 5 (^c/min into 201232893 at this temperature). Thermogravimetric analysis, the thermal loss ° / 〇 / ° C will be reduced to less than 1.0, preferably less than 0.5, and the accuracy is ± 0.005% (% by weight) and ± 0 05. (:. The aromatic polyamidene nanowire is heated in the annealing range for a period of from 5 seconds to 20 minutes, preferably from 5 seconds to 10 minutes. In one embodiment, one is followed by polycondensation from the solution. The PMDA/ODA glutamic acid nanoweb prepared by electrically blowing the nanoweb is heated in a vacuum oven to about 10 ° C to remove residual solvent. After the solvent is removed, the nanometer is removed. The web is heated to a temperature in the range of 300-500 ° C for a period of less than 15 minutes 'preferably less than 1 minute, preferably less than 5 minutes' until at least 90% of the indoleamine function Sexually transformed (醯iminated) is a quinone imine functional 'preferably up to 100% of the enriched amine functionality has been imidized. Then the above-mentioned hydrazine imidized nanoweb is heated The temperature in the range of 400 to 500 ° C is preferably in the range of 400 to 450 ° C, and is heated for a period of 5 seconds to 20 minutes until the crystallinity index is 0.2. The parameter "crystallinity index" used herein. Refers to the relative crystallinity parameter measured by wide-angle ray diffraction (WAXD). This WAXd scan consists of: 1) a background signal; 2) scattering from an ordered but amorphous region; ) scattering from the crystalline region. The ratio of the integral value under the peak identified as the crystallization peak to the integral value of the overall scan curve minus the background value is the crystallinity index. In one aspect, the invention provides an article comprising a nanoweb of an aromatic polyamidene nanofiber, the nanoweb having a surface, at least a portion of the surface comprising a primary guanamine, the secondary The guanamine contains a functional group containing a hydrocarbon radical. The hydrocarbyl radical may be saturated or the olefin is free of its a aromatic substituent. In the embodiment, the hydrocarbyl group is a saturated hydrocarbon. In a further embodiment, the hydrocarbon is a radical. In the further embodiment, the alkyl radical is in the form of a positively charged radical. In the further embodiment, the length of the n-radical radical is in the range of from 1 Torr to 30 carbons. In still another embodiment: In the embodiment, the strand free radical has a length of 15 to 20 carbons. In one embodiment, the functional group further comprises a sulfur-containing functional group. In the further embodiment, the functional group is an amine group. Nanowires, which are suitable for use herein, are composed of randomly overlapping fibers characterized by a free surface area. The free surface area of the nanonet is a surface area that can be contacted by a liquid or gaseous reagent. = The free surface area of the nanoweb is essentially the sum of the surface areas of the individual constituent fibers, minus the areas that are blocked by the overlap of two or more fibers. Methods for directly measuring free surface regions are well known, such as nitrogen adsorption, mercury p〇r〇simetry, and helium pycnometry. For the purposes of the present invention, a suitable polyamidene network is characterized by a porosity of between 2 and 80%. In one embodiment, the porosity is in the range of 3 〇 to 6 〇 0 / 0 0. In another aspect, the invention provides a method for chemically modifying the surface of an aromatic polyamidene network. The method comprises contacting an aromatic polyamidene network with a solution of a primary amine at a contact temperature between room temperature and 150. The range of bismuth, the range of contact is in the range of from 1 to 240 minutes, wherein the primary amine comprises a functional group containing a hydrocarbyl radical. The hydrocarbyl radical may be saturated or olefinically unsaturated, and 201232893 is a nr from A: - an example of an anion radical which is a saturated smoke. In the further embodiment, the hydrocarbon radical. In the further embodiment 'the alkyl di-: diradical form. In a further embodiment, the alkyl group has a length in the range of 10 to 30 carbons. " In the example, the length of the radical-based radical is one step. In one embodiment, the functional group further encapsulates -=°, the functional group of sulfur*> In a further embodiment: 3 or The functional group is an -amino group. The concentration of the invention of gas, milk or sulfur is not particularly limited, and it is found that at the concentration of about 1% by weight or less, there is almost no surface for the polyamidene nanonet at the time of implementation of this month. Observable effect. After the surface of the polyamidene nanoweb is halogenated, the above-mentioned treated nanoweb is rinsed in the sub-toluene to remove the unreacted amine. In some cases, (4) the demander is a polyamidene nanoweb that is aminated. Drying can be at 95. (In one embodiment of the method herein, the concentration of the primary amine solution is in the range of 0.1 to 0-5 Torr. In one embodiment, the period is in the range of 1 to 60 minutes. The solvent of the aliphatic amine solution includes, but is not limited to, hydrazine, hydrazine-di-f-carbamamine, hydrazine, hydrazine-dimethylacetamide, hydrazine methylpyrrolidine, toluene and xylene. In one embodiment, the solvent is hydrazine, hydrazine-dimercaptoamine. Suitable aliphatic amines for use in the practice of the invention include, but are not limited to, octadecylamine, hexadecyiamine or dodecylamine. , hexamethylenediamine, histamine, ethylenediamine. 201232893 In another aspect, the present invention provides a method for filtration, and the two-method method comprises causing a mixture of a solid (tetra) fluid to wetly collide with ^ The surface modified polytheneimine _ surface, such that the mixture = _ containing the fluid portion transported through the surface modified poly phthalimide network and the mixture - the solid portion is not transported through And wherein the surface modified polyamidene network comprises an aromatic poly A nanoweb of an amine nanofiber having a free surface region, at least a portion of the free surface region comprising - a secondary guanamine, the secondary amine comprising a functional group containing a -hydrocarbyl radical. The hydrocarbyl radical may be saturated or olefinically unsaturated and may include an aromatic substituent. In an embodiment, the nicotine radical is a saturated hydrocarbon. In a further embodiment, the hydrocarbon is monoalkyl free. In a further embodiment, the alkyl radical is in the form of a n-alkyl radical. In a further embodiment, the n-alkyl radical has a length in the range of 10 to 30 carbons. In still a further embodiment, the n-alkyl radical has a length of from 15 to 20 carbons. In one embodiment, the functional group further comprises a functional group containing oxygen, nitrogen or sulfur. In a further embodiment The functional group containing oxygen, nitrogen or sulfur is an amine group. In one embodiment of the method, the nanofiber is characterized by a number average diameter of less than 1000 nm, even less than 800 nm, or even about Between 50 nm and 500 nm and even A fiber between about 100 nm and 400 nm. In the case of a non-circular cross-section of nanofibers, the term "diameter" as used herein refers to the largest cross-sectional dimension. 17 201232893 In one embodiment of the method, The aromatic polyimine is a poly-imine. In a further embodiment, the total inferior 'Wang Fang is a PMDA/ODA. The polyamidene network is suitable for the so-called nano mesh. The deep tears, the fine fluid matter is removed from the r fluid stream. In one embodiment: the mixture is picked up from 4 y szT as a gas with particulate matter and the particulate matter, in the gas. In another embodiment The fluid mixture is a liquid of particulate matter and the particulate matter is entrained in the liquid. In a microstep embodiment, the gas is a gas mixture. In still another aspect, the liquid is a liquid mixture. The surface modified imine mesh of the present invention is characterized in that the affinity of the surface for the body 4 is adjusted, depending on the specificity of the hydrocarbon radical of the secondary guanamine, for example, as compared with 爿A The water contact angle of the unreacted aminated surface modified polyamidene network is 1〇5. And in Example 9: after amination with octadecylamine, the contact angle was 146. , 21 ° ^ water significantly increased. The surface modification of this article (four) family of polyimine = : ' is particularly suitable for under the strong conditions and in the special environment. The surface modification of the aryl = amine glutamine network shows that in the presence of water vapor, its swelling is significantly reduced and the ruler shape is also reduced. The transport of the body can be achieved by existing methods such as gravity, pressure and capillary action. In another aspect, the present invention provides a filtering device, the device is provided with a first opening to introduce a pseudo-separating device and a first port to discharge a The fluid is filtered out, and the surface of the shell is modified with an aromatic polyamidene net, which is densely arranged so that the mixture can wetly collide with the surface of the nano-net 201232893 Having a fluid-rich portion of the mixture transported through the surface-modified polyimine mesh, and one of the mixture is enriched in a solid portion and is not transported through the ' and the surface-modified poly-imine The rice mesh comprises a nanoweb containing aromatic polyamidene nanofibers, the nanoweb having a free surface region, at least a portion of the free surface region comprising a primary guanamine - the secondary guanamine comprises a A functional group containing a hydrocarbon radical. The hydrocarbyl radical may be saturated or olefinically unsaturated and may include an aromatic substituent. In one embodiment, the hydrocarbyl radical is a saturated hydrocarbon. In a further embodiment, the hydrocarbon is a monoalkyl radical. In a further embodiment, the alkyl radical is in the form of a n-alkyl radical. In a further embodiment, the n-alkyl radical has a length in the range of 10 to 30 carbons. In yet a further embodiment, the n-alkyl radical has a length of from 15 to 20 carbons. In one embodiment, the functional group further comprises a functional group containing oxygen, nitrogen or sulfur. In a further embodiment, the oxygen, nitrogen or sulfur containing functional group is an amine group. In one embodiment of the filtration device, the nanofibers are characterized by a number average diameter of less than 1000 nm, even less than 800 nm, even between about 50 nm and 500 nm, and even between about 1 〇〇 nm. And between 400 nm fiber. In the case of a non-circular cross-section of nanofibers, the term "diameter" as used herein refers to the largest cross-sectional dimension. In one embodiment of the filtration device, the aromatic polyimine is a wholly aromatic polyimine. In a further embodiment, the wholly aromatic polyimine is a PMDA/ODA. In one embodiment, the filtering device further comprises a rigid support member to prevent the surface modified aromatic polyamidene nanowire from being distorted by the pressure difference of the 19 201232893 non-meter thickness pg. The rigid slab member is an open design structure to allow the expiratory fluid to be freely maneuverable when flowing out of the nanonet n. An embodiment of the susceptor is shown in Figure 224. And define - internal space 12. A suitable; > can be made of any material that is made for a specific application. For a variety of applications, non-recording steel (especially Type 316) is an acceptable housing material. The housing is provided with an input port 13 as shown (the mixed filter to be filtered is introduced through the 5H input port) To the internal space 12), and to pass through the α 14 (the filtered outflow system is supported by the output port and the titer supports the combination of the two layers of the modified polyamidene network 15 and -, The rigid support has an open structure

Li Γ device member 17. The filter member 17 is disposed on the inner portion of the solid and the filter and the fluid, and is conventionally used and sealed by the use of the seal. Any such technology Α ^ 夂 filtration application of the sealing device is suitable for: the sealing device includes. Ring, bracts _ metal white can be n grease and similar. In the case of in-drinking, the term "applicable" should be understood to mean that the filter device must consider the nature of the separation of the mixture to be corroded, cracked or otherwise degraded, and: the pollution of the fluid flow. The invention can avoid the above-mentioned:: iM! 'The present invention provides a multi-layer article: the two-electrode material, the second electrode material and the porous separator disposed between and in contact with it , ^3 a nanoweb containing a plurality of nanofibers, wherein 20 201232893 the nanofiber is mainly composed of an aromatic polyimine. The nanoweb has a free surface region, and the free surface region is at least A portion comprises a first or second guanamine comprising a functional group containing a hydrocarbyl radical. The hydrocarbyl radical may be saturated or olefinically unsaturated and may include an aromatic substituent. In one embodiment, the hydrocarbyl radical is a saturated hydrocarbon. In a further embodiment, the hydrocarbon is a monoalkyl radical. In a further embodiment, the alkyl radical is in the form of a n-alkyl radical. In a further embodiment, the n-alkyl radical has a length in the range of 10 to 30 carbons. In yet a further embodiment, the n-alkyl radical has a length of from 15 to 20 carbons. In one embodiment, the functional group further comprises a functional group containing oxygen, nitrogen or sulfur. In a further embodiment, the oxygen, nitrogen or sulfur containing functional group is an amine group. In one embodiment of the filtration device, the nanofibers are characterized by a number average diameter of less than 1000 nm, even less than 800 nm, even between about 50 nm and 500 nm, and even between about 100 nm and 400 nm. The fiber between. In the case of a non-circular cross-section of nanofibers, the term "diameter" as used herein refers to the largest cross-sectional dimension. In one embodiment of the multilayer article, the aromatic polyimine is a wholly aromatic polyimine. In a further embodiment, the wholly aromatic polyimine is a PMDA/ODA. In one embodiment, the first and second electrode materials are different, and the multilayer articles herein are useful in batteries. In another embodiment, the first and second electrode materials are the same, and the multilayer articles herein can be used in capacitors, particularly a type of capacitor known as an "electronic double layer capacitor." 21 201232893 In one embodiment, the first electrode material is a laminate, the separator, and the electrode material of the first embodiment. In a combination, a paste is applied to form a surface of the nanoweb separator to which the additive is applied. 1. Two opposite surface adhesive laminates. Pressure and/or as formed - in the multilayer article of the invention may be used in the case of a bell ion, the first electrode material being - a negative electrode material comprising - a material for the implementation of u ^ . In the group of -f#, sub-intercalation free carbon, graphite, coal char, material = composite and its mixture. In one to two, the second electrode material is a positive electrode material, which is selected from oxides, hetero-chains, lithium oxides, and acid-acids. MNC (LiMn(1/3) Cg(1) /3) Ni(i/3) Ming Zhong, (L^ The first layer of articles further includes at least one metal that is in adhesive contact with at least one of the mines and the upper ones. The metal material of the electrode material is contacted by the metal (4) (4) ϋ. Each of the 5 hai materials is one of the steps. In the embodiment, the electrode material of the electrode material is not the battery of the electrochemical cell. In the example, the gold machine collects apricots containing different metals. In the capacitor embodiment of the electrochemical cell unit 22 201232893 herein, the metal current collector comprises the same metal. The metal current collector suitable for use in the present invention is preferably Figure 2 depicts an embodiment of the multilayer article of the present invention. Referring to Figure 2, the multilayer article of the present invention depicted therein comprises a porous nanoweb separator 21 which is primarily composed of polyamidene nanofibers. (mainly composed of a wholly aromatic polyimine) Between a negative electrode 22 and a positive electrode 23, each electrode is deposited on a non-porous conductive metal foil 24a and 24b. In one embodiment, the negative electrode 22 comprises carbon 'preferably graphite, and The metal foil 24a is a copper foil. In another embodiment, the positive electrode 23 is a Zhongming oxide 'wall iron iron clock or a fine oxide, and the metal foil 24b is an aluminum foil, and wherein the nano mesh has - a free surface region - at least a portion of the free surface region comprising a primary guanamine comprising a functional group containing a hydrocarbyl radical. The hydrocarbyl radical may be saturated or olefinically unsaturated and may comprise An aromatic substituent. In one embodiment, the hydrocarbyl radical is a saturated hydrazine. In a further embodiment, the hydrocarbyl radical is a monoalkyl radical. In a further embodiment, the alkyl radical is free The base is in the form of a n-alkyl radical. In a further embodiment, the n-alkyl radical has a length in the range of 10 to 30 carbons. In yet a further embodiment, the n-alkyl radical The length is 15 to 20 carbons. In an embodiment, the multilayer article comprises a first layer comprising a first metal current collector; a second layer comprising the first electrode material in adhesive contact with the first metal current collector; a three layer comprising the aromatic polyamidene nanoweb in adhesive contact with the first electrode material, wherein the nano mesh 23 201232893 has a free surface region, at least a portion of the free surface region comprising a second The guanamine contains a functional group containing a hydrocarbon radical. A fourth layer comprising a second electrode material adhesively contacting the aromatic polyimide network. The five layers 'contain a second metal current collector that adhesively contacts the second electrode material. The nicotine free radical can be saturated or olefinically unsaturated and can include a diaromatic substituent. In one embodiment, the hydrocarbyl radical is a saturated fumes. In a further embodiment, the hydrocarbon is an alkyl radical. In a further embodiment, the alkyl radical is in the form of a -n-alkyl radical. In a further embodiment, the length of the n-radical radical is in the range of 10 to 30. In yet a further embodiment, the positively charged radicals are 15 to 20 carbons in length. In the embodiment, the functional group further comprises an oxo group containing oxygen, nitrogen or melon. In a further embodiment, the oxygen, nitrogen or sulfur containing functional group is an amine group. In one embodiment, the first layer is a copper foil and the second layer is a counter rut preferably graphite. In a further embodiment, the third layer of the aromatic polyamidene network is a reinforced aromatic polyamidene network. In a further two-step embodiment, the third layer of the aromatic polyamidene network is a = wholly aromatic polyamidene network. In a further embodiment, the second layer of the wholly aromatic polyamidene network is a reinforced all aromatic polyfluorene, amine nanonet. In a further embodiment, the third layer of the wholly aromatic 'imine nanoweb is PMDA/ODA. In a further embodiment 24 201232893, the third layer of pmda/oda nanonet is an enhanced PMDA/ODA nanoweb. In another embodiment, the four layers are Zhongming Oxide' and the fifth layer is an aluminum foil. In one embodiment, the first layer is a copper foil, and the second layer is carbon, preferably graphite. The third layer is a nano mesh mainly composed of pmda/oda nanofibers. The layer is lithium cobalt oxide and the fifth layer is an aluminum foil, and wherein the nanoweb has a free surface region, at least a portion of the free surface region comprising a primary guanamine, the secondary guanamine comprising a hydrocarbon-containing group a functional group of a radical. The hydrocarbyl radical may be saturated or olefinically unsaturated and may include an aromatic substituent. In one embodiment, the § 烟 radical is a saturated smoke. In a further embodiment, "•海& is a calcined radical. In a further embodiment, the alkyl radical is in the form of a normal alkyl radical. In a further embodiment, the length of the positively charged radical is in the range of 10 to 3 carbons. In yet a further embodiment, the n-alkyl radical is from 15 to 20 carbons in length. In one embodiment, the functional group further comprises a functional group containing oxygen, nitrogen or sulfur. In a further embodiment, the oxygen, nitrogen or sulfur containing functional group is an amine group. In the step-for-step embodiment, both sides of (iv) are coated with the positive or negative electroactive material. This allows - an arbitrary size - and the prismatic stack of voltages can be rapidly formed. The pavement is composed of the light amine adiamine two and the foils having the two sides alternately stacked, as shown in Fig. 3. The stack as shown is generally disposed in a housing 31 which is filled with an electrolyte solution 32. The stack comprises a plurality of interconnected multilayer articles of the invention. The multilayer article is illustrated in Figure 2. Referring to Fig. 3, 25 201232893, a plurality of porous polyimine mesh spacers 21 are stacked with alternating negative electrode layers 22 and positive electrode layers 23. In one embodiment, the negative electrode material 22 is carbon, preferably graphite, and is deposited on both sides of the copper foil 24a, and the positive electrode material 23 is cobalt oxide and deposited on both sides of the aluminum foil 2 And wherein the nanoweb has a free surface region, at least a portion of the free surface region comprising a primary guanamine, the secondary guanamine comprising a functional group containing a hydrocarbon radical. The hydrocarbyl radical may be saturated or olefinically unsaturated and may include an aromatic substituent. In one embodiment, the hydrocarbyl radical is a saturated hydrocarbon. In a further embodiment, the hydrocarbon is a monoalkyl radical. In a further embodiment, the alkyl radical is in the form of a n-alkyl radical. In a further embodiment, the length of the n-alkyl radical is in the range of 10 to 3 carbons. In yet a further embodiment, the n-alkyl radical is from 15 to 2 carbons in length. In one embodiment, the functional group further comprises a functional group containing oxygen, nitrogen or sulfur. In a further embodiment, the oxygen, nitrogen or sulfur containing functional group is an amine group. Another embodiment of the article of the invention is shown in Figure 4a. Referring to FIG. 4a, the article of the present invention comprises a porous nanonet separator 21 suitable for use in the present invention, which is mainly composed of a nanofiber of a wholly aromatic polyimide, and is disposed on a negative electrode 22 and Between a positive electrode 23, each electrode is directly deposited on opposite sides of the nanonet, and wherein the nanoweb has a /free surface region, at least a portion of the free surface region comprising a primary guanamine, the second The guanamine contains a functional group containing a hydrocarbon radical. The hydrocarbyl radical may be saturated or olefinically unsaturated and may include an aromatic substituent. In one embodiment, the hydrocarbyl radical is a saturated 26 201232893. In the embodiment, the fumes are -· radicals. In the case of a ..^, the alkyl radical is a n-alkyl radical, and the length of the di-diyl radical is in the group from the 15 i ^' step, and the positive barrier material is The method well known in the art for deposition on sMJl includes paste extrusion and printing. In one embodiment, the negative charge 3 is preferably graphite. In another embodiment, the positive electrode comprises a lithium diamond oxide, a gamma neodymium (tetra), preferably a sigma oxide. Figure 4a is configured - a further embodiment is shown in Figure 4b, wherein a layer of metal foil 24 is added to the structure of Figure 4a as shown. In the embodiment, the multilayer structure of the pattern is laminated to provide a tight surface contact to the surface and adhesion between the layers. In another aspect, the present invention provides an electrochemical cell comprising a plurality of articles disposed in a housing of the napkin, an electrolyte, and at least partially immersed in the electrolyte; the multilayer article The first electrode current collector, a first electrode material electrically conductively contacting the first metal current collector, and a second electrode material electrically conductively contacting the first electrode material are disposed on the first electrode An aromatic polyamidene nanomesh separator between and contacting the electrode material and the second electrode material; and a second metal current collector electrically conductively contacting the second electrode material, wherein the aromatic The polyimine mesh separator comprises a nanoweb comprising a plurality of nanofibers, wherein the nanofiber is mainly composed of an aromatic polyamine, the nanoweb having a free surface area, 27 201232893 At least a portion of the s-free free surface region comprises a first-stage, captanamine comprising a functional group containing a hydrocarbyl radical. The hydrocarbyl radical may be saturated or dilute hydrocarbon unsaturated and may include an aromatic substituent. In one embodiment, the hydrocarbyl radical is a saturated hydrocarbon. In a further embodiment, the hydrocarbon is a monoalkyl radical. In a further embodiment, the alkyl radical is in the form of a n-alkyl radical. In a further embodiment, the n-alkyl radical has a length in the range of 10 to 30 carbons. In yet a further embodiment, the positively charged radicals are 15 to 20 carbons in length. In one embodiment, the functional group further comprises a functional group containing oxygen, nitrogen or sulfur. In a further embodiment, the oxygen, nitrogen or sulfur containing functional group is an amine group. In one embodiment of the filtration device, the nanofibers are characterized by a number average diameter of less than 1000 nm, even less than 800 nm, even between about 50 nm and 500 nm, and even between about 1 〇〇 nm and Fiber between 400 nm. In the case of a non-circular cross-section of nanofibers, the term "diameter" as used herein refers to the largest cross-sectional dimension. In one embodiment of the electrochemical cell, the aromatic polyamidiamine is a full-scale polyimine. In a further embodiment, the wholly aromatic polyimine is a PMDA/ODA. In one embodiment of the electrochemical cell herein, the first layer of the multilayer article is a copper foil and the second layer thereof is carbon, preferably graphite. In a further embodiment of the electrochemical cell herein, the third layer of the aromatic polyamidene mesh separator comprises a reinforced all aromatic polyamidene nanoweb. In a further embodiment, the third layer of the aromatic polyamidene mesh separator comprises a wholly aromatic polyamidite network. In a further embodiment 28 201232893, the third layer of the wholly aromatic polyamidene mesh separator comprises an enhanced wholly aromatic polyamidene network. In a further embodiment, the third layer of fully aromatic polyamidene nanoweb comprises PMDA/ODA. In a further embodiment, the third layer of the PMDA/ODA nanomesh separator comprises a reluctant PMDA/ODA nanoweb. In another embodiment, the four layers are lithium cobalt oxide and the fifth layer is an aluminum foil. In one embodiment, the first layer is a copper foil; the second layer is carbon, preferably graphite, and the third layer is a nano mesh mainly composed of PMDA/ODA nanofibers, the fourth The layer is a lithium cobalt oxide; and the fifth layer is an inscription, and wherein the nanoweb has a free surface region, at least a portion of the free surface region comprising a primary guanamine, the secondary guanamine comprising a a functional group of a hydrocarbon radical. The hydrocarbyl radical may be saturated or olefinically unsaturated and may include a diaromatic substituent. In one embodiment, the hydrocarbyl radical is a saturated hydrocarbon. In a further embodiment, the hydrocarbon is a monoalkyl radical. In a further embodiment, the alkyl radical is in the form of a n-alkyl radical. In a further embodiment, the length of the n-alkyl radical is in the range of 30 carbons. In a further embodiment, the length of the normal radical is from 15 to 20 carbons. The step comprises an oxygen, nitrogen or oxygen containing oxygen, nitrogen or sulfur. In one embodiment, the functional group is a sulfur functional group. In a further embodiment the functional group is an amine group. In an embodiment of the first 7", in the first-and-earth-and-different embodiment, the first electrode of the electrochemical cell is the same as the first electrode material, 29 201232893 The battery unit is a capacitor, preferably a capacitor. The sublayer bipolar material contains the same chemical composition when it is mentioned herein that the electrode material is (iv). However, 1 table shouts that the isoelectric particle size may be different. For some structural components, please refer to FIG. 3. When the stacked stack (as shown in FIG. 3, the liquid-tight casing 31 is formed, the casing of the present invention can be formed as a metal "can". And containing a liquid = single 32. In a further embodiment, the liquid electrolyte is soluble in (4). In the - step implementation of the wealth = dissolved salt for Lim, LiBF4 or Lie · in - Further examples = S-organic solvent comprises one or more alkyl carbonates. In a further practice, the - or more carbonic acid-containing - carbonic acid mixture is a mixture of esters and esters. The preferred range may vary depending on the material used and the intended use conditions; for example, depending on the intended operating temperature. In one embodiment, the solvent is 70 parts by volume of ethyl carbonate and 30 parts by volume of dimethyl carbonate. An ester which is LipF6. Alternatively, the electrolyte salt may comprise lithium hexafluoroarsenate, bistrifluoromethylsulfonamide clock, lithium bis(oxalate) boronate, difluorooxalic acid a Li+ salt of a bell or polyfluorinated cluster anion (clusterani〇n) or a group of these substances Or 'the electrolyte solvent may include an ester of propylene carbonate, ethylene glycol or poly(ethylene glycol), an ether or a trimethyl sulfonium derivative or a combination of these substances. Further, the electrolyte may contain a known Various additives for improving the stomach b or stability of Li ion batteries, for example, reviewing k. Xu in

Chem. Rev., 104, 4303 (2004), and S.S. Zhang in J. Power Sources, 162, 1379 (2006). 30 201232893 With respect to the stacked stack, the stack illustrated in Figure 3 can be replaced by the multilayer article depicted in Figure 2. Also appearing but not shown is the means for connecting the battery unit to an external electrical load or charging device. Suitable devices include wires, pole tips, connectors, plugs, clips, and the like that are used to create electrical connections. If individual cells in the stack are electrically connected to each other in series, from positive to negative, the output voltage of the stack is equal to the combined voltage of each battery cell. If the individual battery cells that make up the stack are electrically connected to each other in parallel, the output voltage of the stack is equal to the voltage of a single battery cell. One of ordinary skill in the art of electric motors will know when it is appropriate to arrange in series, and when it is arranged in parallel. Lithium-ion batteries come in many forms, including cylindrical, prismatic, pouch, coiled, and laminated. Lithium-ion batteries have been found to be used in a variety of different applications (eg, consumer electronics, power tools, and hybrid vehicles). Lithium-ion batteries are manufactured in a similar manner to other batteries such as NiCd and NiMH but are more sensitive because of the reactivity of the materials used in Li-ion batteries. The positive and negative electrodes in a lithium ion battery cell suitable for use in an embodiment of the present invention are similar in form to one another and are fabricated on similar or identical equipment in a similar process. In one embodiment, the active material is applied to both sides of a metal foil, preferably an A1 foil or a Cu foil, which acts as a current collector to conduct current into and out of the battery cells. In one embodiment, graphite carbon is applied to a copper foil to prepare a negative electrode. In one embodiment, a lithium metal oxide (e.g., LiCoO 2 ) is coated on an Ai foil to prepare a positive electrode. In a further embodiment, the foil coated as described above is wound onto a large reel 31 201232893 and placed in a drying chamber for cell fabrication. Referring to FIG. 5, for each electrode, the active material binder solution 52 and the conductive filler 53 (if the composition formed on the F1 is transmitted through the precision adjuster 54 into the I mix tank 55') Mixing therein to produce a "sequential appearance" agent including, but not limited to, poly(difluoroethylene) homopolymer and mound, styrene butadiene rubber, polytetrafluoroethylene, and polyaniline II The slurry formed as above is then fed or pressure fed to %' which is passed through 57 and sent to a coating head 58. The coating head deposits a controlled amount of polymer on a movement The surface of the metal is dropped, and the 5th metal foil is fed from a feed 510. The town coated as above is conveyed through a series of rolls 511 through an oven 512, which is set at 1 to 150 Torr. The edge 513 of the inlet of the flood box is located at an adjustable distance above the crucible; the thickness of the electrode formed thereby is adjusted by adjusting the gap between the edge and the foil. In the oven, the solvent is generally passed through a solvent. The unit 514 is volatilized and then evaporated. It is sent to a winding pro 515. The thickness of the electrode after drying is generally in the range of 5 〇 to 15 〇 micrometer. If a coating is produced on both sides of the foil, the one-side coated foil formed as above is Feed into the coater, but the uncoated side is configured to receive the slurry deposit. After coating, the electrode formed as above is then calendered and selectively cut into narrow strips for batteries of different sizes. Any burrs on the edge of the foil strip may cause internal breaks in the battery unit, so the cutter must be manufactured and maintained very precisely. 32 201232893 In the electrochemical cell of the present invention - the pole assembly is - for a cylindrical battery Single_?=., the electric power of this paper is applicable to the spiral winding structure of the screw Λ 70. - The embodiment wire (4) h is in a stack structure, which is suitable for the prism. The pile similar to the one in Fig. 3 can be made into a coil. Form: in the == single unit is also made in a single can,: = push = in order to form one of the invention Li ion Ray from the time - for example, the electrode assembly is firstly rolled A 1 solid column type is suspected first Winding into a spiral surnamed two as shown in Figure 6, 'after a pole A handle is applied to the edge of the electrode to connect the electrode to the terminal of the i ^. In the case of a high power battery unit, the user needs to carry a high current using a plurality of poles welded along the edge of the electrode strip. The handle is welded to the can body, and the electrode-rolling member of the slewing coil is inserted into the cylindrical-shaped shell. Then the casing is sealed, but left: one open: for injecting the electrolyte into the casing. Electrolysis f is filled into the battery unit and the battery unit is sealed. The electrolyte is usually a mixture of a salt (LiPF6) and a carbonate-based solvent. The assembly of the gas battery unit is preferably carried out in a "drying chamber" because of the electrolyte It reacts with water. Moisture can cause LipF6 to hydrolyze to form HF, which can degrade the electrode and adversely affect the performance of the battery unit. After the battery unit is assembled, it is subjected to at least one precisely controlled charge/discharge cycle to activate the working material to form (activate) it. For most lithium ion chemistries, this involves the creation of a SEI (solid electrolyte interface (s〇iid eieetr〇iyte 33 201232893 interface)) layer on the negative (carbon) electrode. This is a passivation layer and is not important for the electrolyte step-by-step reaction. (The fossil is in contrast to the other, and the present invention provides a Dic volume of an electrochemical double enthalpy). . ^2 energy storage device, which has ^ 达 = charge storage in a double-layer electrochemical capacitor, such as the occurrence of the interface between the electrode ("carbon") and the electrolyte in the two-layer capacitor The ugly imine nano, ..., is a separator that absorbs and retains the electrolyte by maintaining intimate contact between the electrolyte and the electrode. The role of the aromatic polyamidene nanowire as the separator is to electrically isolate the positive electrode from the negative electrode to facilitate the transfer of the electrochemical double layer capacitor in the electrolyte during charge and discharge. A cylindrical winding design was fabricated in which two carbon electrodes and a separator were wound up, and the aromatic polyamidene mesh separator had high strength to prevent short-circuiting between the two electrodes. The invention is further illustrated by the following specific examples, which are not limited thereto. Examples 1 to 8 and Comparative Example A Polymer preparation [HMT E115199_39PI = polymer 2u〇9, spin-spun SF44P1DBX001D15IR20IM501] PMDA and 〇DA poly-aracine in DMF solvent were prepared according to industrial standard method and over 4〇da , with 97% stoichiometry and 23% solids by weight. The polyamidoxime was blocked with 0.04% by weight of phthalic anhydride (required to confirm the wt% of the terminal blocking agent). 34 201232893 Nanoweb Preparation The PAA solution prepared above was poured into the apparatus shown in Fig. 7. Figure 7 illustrates an embodiment of a suitable electroblowing device. The polylysine solution was spun into a nanofiber (electric blown f as described in our provisional application) at 34 at a solution pressure of 5.5 bar. . The temperature is at a temperature of 55 C and at a speed of 5833 m/min. The resulting nanoweb had a thickness of 21 to 26 microns and a porosity of 63%. Referring again to Figure 7', the nanoweb 1〇5 was passed through a hot air dryer 1〇7 at 180 C for 1.13 minutes. The dried nanoweb as above is then wound into a roll. The polyamidite mesh prepared as above was then unwound and subsequently imidized by heating to a temperature of about 325 in a Glenro mid-band infrared oven for 0.87 minutes and coiled again. The web was then unwound and calendered on a BF Perkins calender, which was carried out between a stainless steel calender roll and a cotton covered calender roll at a pressure of 2,700 pounds per linear inch and then wound again. The calendered web was then unwound, subjected to a second heat treatment at about 450 ° C for 6 minutes, and wound again. Amidation and test results A sample of the eight polyamidene nanofiber webs prepared as above (each weighing approximately 35 mg) was added to 5.0 gm octadecylamine (Aidrich 305391) in 100 mL of anhydrous N. In the preheated solution of N-dimethylformamide (DMf) (Aldrich 227056), the addition was carried out in nitrogen in a Pyrex vessel equipped with a heating pack. After each period indicated in Table 1, a sample was removed from 35 201232893 at the indicated solution temperature and rinsed four times in toluene at % = dry for 1 hour in a vacuum oven. Keep an untreated starting material sample for each sample's attenuation of the infrared spectrum (継服) = octa group and human on the sample surface, as indicated by the absorption peak at 292Gem-i (due to Aliphatic CH stretching mode), relative to the intrinsic absorption peak (due to the aromatic CH stretching mode). The aliphatic group =, ° S is also accompanied by a broad absorption at 3360 cm·1, which forms a -9 with the first and second grades. These measurements, as summarized in the table, show that the reaction rate is significantly reduced after 60 minutes. As shown in Table 1, as the binding of octadecylamine increased, the static contact angle of the deionized water on the nanometer was 104.7. Increase to 146.8. , showing: an intermittent hydrophobic surface, and its mass is only increased by 2 5%, which corresponds to ^ 0. 〇 39 equivalents of octadecylamine group / polyimidazolium. Although there is no restriction on the invention 4, it is believed that this data is related to the -mode result, in which the reaction mainly occurs on the surface of the nanofiber and the core of the 5 meronimide fiber is relatively unaffected. change.

36 201232893 8 η μ 180 153E-02 137 9 9 υ ιι .1 . 240 2.13E-02 146.8 * Absorption at 2920 c (normalized to 309 η at 3092 cm-1) -1 -, -III :i--j Multiple samples of Comparative Example A and Example 9 were examined by scanning electron microscopy 'as shown in Figures 8a and 8b, respectively. No differences attributable to treatment with octadecylamine were found in the fiber morphology or tissue gap. Examples 10 and 11: Polyamidene meshes partially amidated with n-alkylamine. 5 g of n-dodecylamine was dissolved in 1 mL of DMF solvent. A sample of the polyimine mesh of Example 1 was immersed in the solution at 50 ° C for a period of 1 hour and 20 hours, respectively. The samples were simultaneously immersed, removed after different time intervals, and then rinsed three times with isopropanol. Scanning electron microscopy revealed that the fiber morphology was unchanged compared to the unreacted control group. The diffuse reflectance infrared spectrum showed an absorption peak at 2852 and 2919 cm-1, which confirmed an aliphatic group. A secondary guanamine group was confirmed at the absorption peaks of 1545, 1650 and 3267 cm-1. The infrared spectrum of the reaction product retains a strong absorption peak of the original polyimine at 1700 and 1500 cm-1, meaning that the oximation reaction is mainly limited to the thin layer polymer on the surface of the nanofiber. Examples 12 and 13: Polyamidylene nets partially amidated with n-alkylamine. 37 201232893 A solution of 5% by weight of n-hexadecane in DMF was prepared. The polyimine mesh sample of Example 1 was immersed in the solution under (10) for a period of 1 hour and 20 hours, respectively, and then rinsed twice with isopropanol. Scanning electron microscopy revealed that the fiber morphology was unchanged compared to the unreacted control group. The diffuse reflectance infrared spectrum showed an absorption peak at 2852 and 2919 cm-1, which confirmed the presence of an aliphatic group. A secondary guanamine group was confirmed at the absorption peaks of 1545, 1650 and 3267 em-1. The infrared spectrum of the reaction product retains a strong absorption peak of the original polyimine at 17 Å and 15 Å cm_i, meaning that the amide amination reaction is mainly limited to a thin layer polymer on the surface of the nanofiber.

Examples 14-17 and Comparative Example BD Two 1" x 3" wide strips were cut from the decylamine mesh of Examples 10-13 and dried overnight in a vacuum oven at 9 (TC). The dried sample was bonded to an electrochemical button type battery. The Li ion button type battery (CR232) was assembled using the following components, which were dried overnight in a vacuum chamber at 9 (TC) obtained from Pred Materials International. NY, NY 10165. The anode and cathode respectively comprise natural graphite coated on a Cu foil and a layer of LiCoO 2 coated on the A1 foil. The electrolyte is contained in a 70:30 mixture of decyl carbonate and ethyl carbonate. 1 molar concentration LiPF6 (Ferro Corp., Independence, OH 44131) 〇

The anode and cathode were separated by a single layer of Example 10-13 amide aminated polyimide mesh having a thickness of 15-25 microns. Connect the Li ion button type battery assembled as above to a battery tester C Series 4000, Maccor Inc., 2805 W. 40 th St., Tulsa, OK 38 201232893 74107) and know by 〇25 It was activated by cycling three times from 2.75 to 4.2 V. Then at 2 capacity retention rate. In the 1 〇C scene, 250 cycles were performed to measure the rate capability, wherein the discharge capacity to 2.75 was measured by -^ ^ ^, and the eight clothes returned to the total battery-single-steady-= electric hunger in just one hour. The capacity at the 250th cycle is considered as an indicator of the stability of the battery. The results are summarized in Table 2.

Discharge capacity at 23 ° C Example Mazur Notebook (mAh ) Surface functionality at 1C Rate at 250 °C or coating solution soaking time (minutes)

Sub-cycle 2.08 1.94 2.07 1.97 2.02 1 - HMT-061009-25-1 ( 26 μηη, porosity 63%) 2-P1.DBX-001-D15-IR20-02-IM5-01 (21 μηι, porosity 60%)丨3 - SF-4-DCQ-001-IR550-N60 I Loss 30-35% 38*40% 38% 64% 28% 43% Example 18-21 Poly(proline) solution 2 (ΡΑΑ2) Preparation A PMDA/0DA polyglycolic acid in DMF and a stoichiometric amount of 97% and a solids weight of 23.5 Å/〇 by weight are confirmed by weight). 0.04% of phthalic anhydride was finalized. The proline seal was blocked (required 39 201232893 Nanonet # 2 (KW-2). The PAA solution prepared above was poured into the apparatus shown in Figure 7 to depict an embodiment of a suitable electroblowing apparatus. Spinning the polylysine/liquid into a nanofiber web (provisional application by ours. The electric blowing procedure of the case) is based on a solution pressure of 5.5 bar at 37 C. Under the program gas temperature of 72 ° C and at a speed of 5833 meters / minute. After that, manually unwind the nano net and use a manual hob cutter to make it about 12 long and 10" A wide hand sheet. The resulting nanoweb is characterized by a porosity of 85 ± 5 〇 / 〇 and a basis weight of 18 ± 2 g / m 2 . Example 18 and Comparative Example E „ with histamine The partially amided polyamidene network will be 2 x 2 of the nanoweb formed as above, and the sample will be imidized and annealed in an air convection oven under 35(): for a minute, and 45〇t:

Go back, two minutes. A sample of the above ruthenium imidized and annealed was placed in a 20 mL glass scintillation vial with 1 mL of a dioxic broth and sonicated for 15 minutes in a Brans〇n sonication bath. The sonicated sample as above was removed and dried in nitrogen in a vacuum oven at 100 ° C for 10 minutes. A solution of histamine (Aldrich) was prepared in a 1 〇〇 mL glass beaker at a concentration of 〇 6 Μ (in ethanol). Solid histamine was added to the glass beaker and ethanol was added with stirring to reach a final concentration of 0_06 Torr. The dried nanoweb as above was immersed at 5 〇〇c for 40 201232893 in the histamine solution for 1 hour. The soaked nanoweb sample as above was removed, dried in nitrogen in a vacuum oven at 100 for 1Q minutes, then placed in a butterfly bottle filled with 1 mL of ethanol, and in a Brans〇n sonication bath (sonicati) Sonication in 〇nbath) for 15 minutes. The sonicated sample as above was removed and dried in nitrogen in a vacuum oven at 100 ° C for 10 minutes. The presence of the amidated surface product was confirmed by FTIR analysis and the attenuated total reflectance (ATR) annex, which was confirmed by the appearance of the characteristic absorption at 2920 cm-1 and 2850 cm-1. And contact angle analysis was performed. The non-melamined nanoweb control group (Comparative Example E) showed a static water contact angle of 15 〇〇 ± 4, while the histamine treated sample showed a static water contact angle of 〇. It was observed that water droplets would penetrate completely into the structure. Each data point is the average of at least three trials. Example 19 - Polyamidinonet net partially partially aminated with N,N diethylethylenediamine. The procedure of Example 18 was repeated on a 2 X 2" sample of a more Example 18 nanoweb, except that the histamine solution of Example 18 at 06M was from 〇〇86 Μ of N,N-diethylethylenediamine (Aidrich). The company was replaced by a solution in ethanol. The presence of the amidated surface product was confirmed by FTIR analysis and attenuated total reflection attachment, which was confirmed by the characteristic absorption at 2920 cm-丨 and 285〇cm-i. The N,N-diethylethylenediamine treated sample showed a static water contact angle of 〇. Example 20: Polyamidene nanonet net partially amided with hexamethylenediamine 201232893 In more Examples 18 2 quot 2" The procedure of Example 18 was repeated on the sample, except that the histamine solution of Example 〇.06 M was replaced by a solution of hexamethylenediamine (Aldrich) in ethanol. And the soaking time was 20 hours instead of 1 hour of Example 18. The presence of the amide surface product was confirmed by FTIR analysis, as in Example 18. The contact angle analysis was performed. The sample treated with hexamethylenediamine showed The static water contact angle is 0°. Example 21: will be based on examples 18, 19 A 6 mg (about 2 cm χ 2 cm) aliquot of each of the prepared lysine nanoweb samples and a 6 mg aliquot of the non-melamine control group were individually filled to 2 In a pasteur pipette, an aliquot of 0 20 niL of deionized water is added to each kerchief, and the recorded water flows through the nanoweb, and the time required to fill the column is 4 hours later. No water flow through: = Dropper for the sample preparation. The water completely flows through the dropper filled with the materials prepared in Examples 18, 19 and 2G within 10 minutes. [Simplified illustration] Figure 1 An embodiment of a multi-layered article of the present invention is illustrated in Figure 2. Figure 3 is a perspective view of a multi-layered article of the present invention. Illustrative of the further embodiment 42 201232893 Figure 5 is a schematic view of an apparatus suitable for use in preparing a multilayer article of the present invention. Figure 6 is a spiral embodiment of a multilayer article of the present invention. Figure 7 is a diagram for preparing the polyaluminum. Schematic diagram of an electric blowing device of the amine nanonet, which is suitable for implementing the hair Figure 8a shows a scanning electron micrograph of a non-melamined polyamidene network. Figure 8b shows a scan of the lysine of Figure 8a. Electron micrograph. 43 201232893 [Explanation of main component symbols] 11.. Housing 12.. Internal space 13. Input port 14.. Output port 15.. Nano network 16.. Support member 17 . . . filter member 18 . . . seal 21.. . separator 22 .. negative electrode 23 .. positive electrode 24 a ... metal foil 24 b ... metal 24 .. metal foil 31 .. . housing 32.. electrolyte solution 51.. active material 510.. feed roller 511.··roller 512.. oven 513.. knife edge 514.. solvent recovery unit 515.. Winding roller 52.. Adhesive solution 53.. Conductive filler 54.. Precision adjuster 55.. Mixing tank 56.. Pump 57.. Filter 58.. . Coating head 201232893 59.. . Metal foil 105.. nano network 107.. . hot air dryer

Claims (1)

201232893 VII. Patent Application Range: 1. A multi-layer article comprising a first electrode material, a second electrode material and a porous separator disposed between and in contact with the first and second electrode materials Wherein the porous separator comprises a nanoweb comprising aromatic polyamidene nanofibers, the nanoweb having a free surface region, at least a portion of the free surface region comprising a primary guanamine, the second The guanamine contains a functional group containing a hydrocarbon radical. 2. The article of claim 1 wherein the functional group further comprises a functional group comprising oxygen, sulfur or nitrogen. 3. The article of claim 2, wherein the functional group is an amine. 4. The multilayer article of claim 1, wherein the nanofibers are characterized by a number average diameter ranging from 50 to 500 nanometers. 5. The multilayer article of claim 1 wherein the hydrocarbyl radical is a saturated hydrocarbyl group. 6. The multilayer article of claim 1 wherein the hydrocarbyl radical comprises an n-alkyl radical having from 15 to 20 carbon atoms. 7. The multilayer article of claim 1 wherein the aromatic polyimine is a wholly aromatic polyimine. The multi-layer article of claim 1, wherein the first and second electrode materials are different ". 9. The multilayer article of claim 1 wherein the first and second electrode materials are the same. The multi-layer article of claim 1, wherein the first electrode material is a negative electrode material selected from the group consisting of carbon, graphite, coal char, lithium titanate, Li-Sn alloy, Si, C -Si composite materials and their mixtures are composed of a group. The multi-layer article according to claim 1, wherein the second electrode material is a positive electrode material. The positive electrode material is selected from the group consisting of lithium cobalt oxide, iron phosphate clock, nickel oxide, lithium manganese phosphate, and phosphoric acid. A group consisting of cobalt lithium, MNC (LiMn(l/3) C〇(l/3) Ni(l/3) 02), lithium manganese oxide and a mixture thereof. The multi-layer article described in the above paragraph 1 further comprises a metal current collector in occupant contact with each of the electrodes. 13. The multilayer article of claim 12, comprising: a first layer comprising a copper foil; and a second layer comprising graphite in adhesive contact with the copper foil. comprising PMDA/〇DA nanofibers And contacting the stone with one of the nanowebs, wherein the nanoweb has a surface region from 47 201232893, and at least a portion of the free surface region comprises a second amine, the secondary amine containing one a n-octadecyl group; a fourth layer comprising a lithium cobalt oxide adhesively contacting the aromatic polyamidene nanonet; and a fifth layer comprising an adhesive contact The name of the electrode material. 14. The multilayer article of claim 1 which is in the form of a prismatic stack. 15. The multilayer article of claim 1 which is in the form of a spiral stack. 48