Surfactant-coated separator

Abstract

The present invention provides a battery separator comprising a porous membrane with a surfactant coating that effectively reduces water loss while minimizing or eliminating the drawbacks associated with the use of nonionic surfactants. [Solution] A battery separator is provided, comprising a porous membrane and a surfactant on at least one side of the porous membrane, wherein the surfactant comprises a mixture of at least one ionic surfactant and at least one nonionic surfactant.

Description

Technical Field

[0001] This application relates to an improved surfactant-coated separator. Specific types, amounts, and blends of surfactants are used to create an improved surfactant-coated separator.

Background Art

[0002] Automotive technology has advanced by leaps and bounds in the previous century, which has led to the battery being required to develop and operate under very strict new guidelines. These new guidelines have brought about many advancements, including enhanced flooded batteries (EFBs) and idle-stop-start (ISS) batteries. However, the movement towards both of these new types of batteries has caused new problems related to the volume loss of the electrolyte, or what is commonly referred to in the industry as "water loss". In lead-acid batteries, water can be lost due to various factors. One is the electrolysis of water due to overcharging. Also, the use of carbon in the negative electrode can further amplify the effects of water loss. Carbon is a common component in the battery industry for controlling charge acceptance and sulfation.

[0003] To address these water loss problems, certain nonionic surfactants have been used in battery separators. See, for example, the disclosure in Patent Document 1 (International Publication No. 2016 / 138369), which was transferred to Dalamic and is incorporated herein by reference in its entirety. These nonionic surfactants are thought to act to reduce water loss by increasing the overpotential that normally occurs during the electrolysis of water. However, the use of these nonionic surfactants has several drawbacks. One drawback is that the use of nonionic surfactants results in reduced dynamic charge acceptance. While we do not wish to be bound by any particular theory, this is thought to be because the surfactant forms a barrier at the negative electrode, hindering charge acceptance. Another drawback is the increased formation of a dark-colored residue in batteries utilizing these nonionic surfactants. This residue is thought to consist of stearates and / or palmitates. Finally, these nonionic surfactants are thought to cause foaming when exposed to the acid in the battery. Foaming is a problem for battery companies, especially those that use a two-step process for battery formation. The foaming of acids can cause safety problems because bubbles may seep out, and it also reduces visibility. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] International Publication No. 2016 / 138369 [Overview of the project] [Problems that the invention aims to solve]

[0005] Therefore, even when using nonionic surfactants to reduce water loss, it is desirable to minimize or eliminate some of their drawbacks. [Means for solving the problem]

[0006] This specification describes surfactant blends that effectively reduce water loss while minimizing or eliminating the drawbacks associated with the use of nonionic surfactants. The surfactant blends described herein include nonionic and ionic surfactants, and when applied to battery separators inserted into batteries, the resulting batteries exhibit reduced water loss and improved oxidation resistance, particularly the charge acceptance typically caused by nonionic surfactants. To reduce or eliminate the decline in sexual performance.

[0007] In one embodiment, a battery separator is described comprising 1) a porous membrane and 2) a surfactant coating comprising a nonionic surfactant and an ionic surfactant. In some preferred embodiments, the basis weight of the nonionic surfactant on the porous membrane is 10 g / m². 2 The following, or 7g / m 2 The following applies: In some preferred embodiments, the basis weight of the nonionic surfactant is 1 g / m². 2 ~5g / m 2 , 1g / m 2 ~4g / m 2 , or 2.5g / m 2 ~4g / m 2 The ionic surfactant may be present on the porous membrane in an amount of 0.5 wt% to 5.0 wt% or 1.0 wt% to 3.0 wt% based on the weight of the separator.

[0008] In some preferred embodiments, the porous membrane may be a porous membrane made of polyethylene. The porous membrane may be microporous. The porous membrane may be a porous membrane, a woven fabric, a nonwoven fabric, or a combination of the above.

[0009] Nonionic surfactants are not particularly limited and include aliphatic alcohols, cetyl alcohol, stearyl alcohol, pentaethylene glycol monododecyl ether, polyoxypropylene glycol alkyl ether, polyoxyethylene glycol, octylphenol ether, polyoxyethylene glycol alkyl ether, octaethylene glycol monododecyl ether, polyoxyethylene glycol alkylphenol ether, polyoxyethylene glycol sorbitan alkyl ester, oleyl alcohol, polyethylene glycol block copolymer, polypropylene glycol block copolymer, glucoside alkyl ether, decyl glucoside, lauryl glucoside, octyl glucoside, nonoxynol-9, glycerol alkyl ester, polysorbate, sorbitan alkyl ether The surfactant may be at least one selected from sterols, glyceryl laurate, cocamide, costearyl alcohol, metharyl-capped nonionic surfactants, polyol fatty acid esters, polyethoxylate esters, polyethoxylate aliphatic alcohols, alkyl polysaccharides, alkyl polyglucosides, amine ethoxylates, sorbitan fatty acid ester ethoxylates, organosilicone surfactants, ethylene vinyl acetate terpolymer, ethoxylate alkylaryl phosphate esters, sucrose fatty acid esters, polyethoxylate alcohols, polyethylene oxide, acid-soluble sugars, sucrose fatty acid esters, organic fatty acids, hydroxyl acids, nonionic surfactants, octylphenol ethoxylate surfactants, octylphenol ethoxylate nonionic surfactants, and combinations thereof.

[0010] In some embodiments, the nonionic surfactant is a nonionic surfactant having a cloud point higher than about 15°C, higher than about 20°C, or higher than about 25°C.

[0011] In some embodiments, the nonionic surfactant may have the following chemical formula structure.

[0012] [ka]

[0013] In the above structure, n may be an integer between 5 and 20 or between 9 and 17, m may be an integer between 1 and 15 or between 6 and 10, and p may be an integer between 0 and 10 or between 0 and 7.

[0014] Ionic surfactants may also be cationic surfactants, anionic surfactants, or amphoteric surfactants.

[0015] In some embodiments, the ionic surfactant is sulfate, alkyl sulfate, ammonium lauryl sulfate, sodium lauryl sulfate, alkyl ether sulfate, sodium laureth sulfate, sulfonate, docusate, sodium dioctyl sulfosuccinate, alkylbenzene sulfonic acid, phosphate, alkyl ether phosphate, carboxylate, alkyl carboxylate, fatty acid salt, sodium stearate, sodium lauroyl sarcosinate, alkyltrimethylammonium, cetylpyridinium, polyethoxylated taluamine, benzalkonium, benzethonium, dimethyldioctadecylammonium The material may be at least one selected from dioctadecyldimethylammonium salts of alkylsulfonic acids, alkylarylsulfonates, alkylphenol-alkylene oxide addition products, soaps, alkyl-naphthalene-sulfonates, anionic sulfosuccinates, and one or more sulfosuccinates, dialkyl esters of sulfosuccinates, amine compounds (primary, secondary, tertiary, or quaternary amines), block copolymers of ethylene oxide and propylene oxide, various polyethylene oxides, mono and dialkyl phosphate ester salts, and mixtures thereof.

[0016] In some embodiments, an ionic surfactant may be an anionic surfactant having the following chemical formula structure.

[0017] [ka]

[0018] In the above chemical formula, n is an integer from 0 to 10, m is an integer from 0 to 10, n and m can be the same or different, q is an integer from 0 to 10, r is an integer from 0 to 10, s is an integer from 0 to 10, and q, r, and s can be the same or different. R1 is H, a linear or branched saturated or unsaturated alkyl group having 1 to 10 carbon atoms, an aliphatic alcohol having 1 to 10 carbon atoms, an alcohol having 1 to 10 carbon atoms, or an aromatic group. And R2 is H, a linear or branched saturated or unsaturated alkyl group having 1 to 10 carbon atoms, a linear or branched saturated or unsaturated aliphatic alcohol having 1 to 10 carbon atoms, a linear or branched saturated or unsaturated alcohol having 1 to 10 carbon atoms, or an aromatic group. n and m can be the same or different, R1 and R2 can be the same or different, R3 is a hydrogen or methyl group, R4 is a hydrogen or methyl group, R3 and R4 can be the same or different. And X is SO3 - , COO - , PO4 -2 , and similar negatively charged groups. There are also positively charged counter ions for the anionic surfactant, such as Na + , K + , Li + , NH4 + , Ca 2+ , Mg 2+ , and at least one of the like may be included.

[0019] In some embodiments, the ionic surfactant can be an anionic surfactant having the structure of the following chemical formula.

[0020]

Chemical formula

[0021] In another embodiment, a battery separator described herein may exhibit at least one of the following: a perox80 value of 90% or more, 91% or more, 92% or more, 93% or more, 94% or more, 95% or more, 96% or more, 97% or more, 98% or more, 99% or more, or 100% of the initial value before the perox80 test, and an ERBOIL value of less than 60.

[0022] In another embodiment, a lead-acid battery is described comprising 1) a battery separator as described herein and 2) at least one grid comprising lead or a lead alloy, wherein the grid exhibits reduced grid corrosion compared to a battery comprising a battery separator not disclosed herein, i.e., a battery separator whose surface is not coated with the surfactant blend described herein. In the ERBOIL test, the separator is exposed to boiling water for 10 minutes, then immersed in sulfuric acid for 20 minutes. After this, the electrical resistance (ER) is measured.

[0023] In another embodiment, the lead-acid battery is described as comprising a battery separator as described herein, wherein the battery has a black residue rate of less than 3 or less than 2.

[0024] In another embodiment, a lead-acid battery is described in which the lead-acid battery includes a battery separator as described herein, and the battery exhibits improved partially charged state (PSOC) cycle life test results. The PSOC cycle life test results are compared to those of a battery having a separator that does not contain the surfactant blend described herein.

[0025] In another embodiment, a battery separator comprising a porous membrane and a surfactant coating containing a nonionic surfactant on at least one side of the porous membrane, wherein the basis weight of the nonionic surfactant coating is 1 g / m² 2 ~5g / m 2 A battery separator is described herein. The basis weight of the nonionic surfactant coating is 2 g / m². 2 ~4g / m 2 , or 3g / m2 ~4g / m 2 This may also be the case. Compared to separators with high concentrations of nonionic surfactants, this battery separator may exhibit at least one of the following: longer discharge life, less water loss, improved charge acceptance, and longer lifespan.

[0026] In another embodiment, a battery separator comprising a porous membrane and a surfactant coating is described. In this embodiment, the surfactant of the surfactant coating consists of a compound having the structure of the following chemical formula.

[0027] [ka]

[0028] In the above chemical formula, n is an integer from 0 to 10, m is an integer from 0 to 10, n and m are the same or different, R1 is H, a linear or branched saturated or unsaturated alkyl group of C1 to C10, an aliphatic alcohol of C1 to C10, an alcohol of C1 to C10, or an aromatic group, R2 is H, a linear or branched saturated or unsaturated alkyl group of C1 to C10, a linear or branched saturated or unsaturated aliphatic alcohol of C1 to C10, a linear or branched saturated or unsaturated alcohol of C1 to C10, or an aromatic group, n and m are the same or different, R1 and R2 are the same or different, R3 is hydrogen, a methyl group, or an alkyl group of C1 to C5, R4 is hydrogen, a methyl group, or an alkyl group of C1 to C5, R3 and R4 are the same or different, and X is SO3 - COO - , PO4 -2 , and similar negatively charged groups, or positively charged counterions. In some embodiments, R3 and R4 are identical and both are hydrogen. In some embodiments, R3 and R4 are identical and both are methyl groups. In some embodiments, X is SO3 - In some embodiments, X is the COO -In some embodiments, X is PO4 -2 In some embodiments, m and n are integers from 1 to 5 or from 6 to 10, respectively. In some embodiments, n is an integer from 1 to 5 or from 6 to 10. In some embodiments, m is an integer from 1 to 5 or from 6 to 10. In some embodiments, q is an integer from 1 to 10, 1 to 5, or from 6 to 10. In some embodiments, r is an integer from 1 to 10, 1 to 5, or from 6 to 10. In some embodiments, s is an integer from 1 to 10, 1 to 5, or from 6 to 10. In some embodiments, the surfactant has the structure of the following chemical formula.

[0029] [ka] [Effects of the Invention]

[0030] This specification describes surfactant blends that effectively reduce water loss while minimizing or eliminating the drawbacks associated with the use of nonionic surfactants. The surfactant blends described herein include nonionic and ionic surfactants, and when applied to battery separators inserted into batteries, the resulting batteries exhibit reduced water loss and improved oxidation resistance, particularly reducing or eliminating the reduction in charge acceptance typically caused by nonionic surfactants. [Brief explanation of the drawing]

[0031] [Figure 1] Figure 1 is a graph comparing the black residue rates in the embodiments described herein. [Figure 2] Figure 2 is an image showing grid corrosion in some embodiments described herein. [Figure 3] Figure 3 shows the decrease in lattice mass after a specific period of time in the embodiments described herein. [Modes for carrying out the invention]

[0032] Battery separator 1 In one embodiment, a battery separator is described comprising 1) a porous membrane and 2) a surfactant coating comprising a nonionic surfactant and an ionic surfactant. In some preferred embodiments, the basis weight of the nonionic surfactant on the porous membrane is 10 g / m². 2 Below or 7g / m 2 The following applies: In some preferred embodiments, the basis weight of the nonionic surfactant is 1 g / m². 2 ~5g / m 2 , 1g / m 2 ~4g / m 2 , or 2.5g / m 2 ~4g / m 2 The ionic surfactant may be present on the porous membrane in an amount of 0.5 wt% to 5.0 wt% or 1.0 wt% to 3.0 wt% based on the weight of the separator.

[0033] porous membrane In some preferred embodiments, the porous membrane may be microporous, macroporous, mesoporous, or nanoporous. In some preferred embodiments, the average pore size of the porous membrane is 1 micron or less.

[0034] The composition of the porous membrane is not particularly limited and may or may not contain polymers.

[0035] If the porous membrane is a polymer, it may have a composition comprising at least one of the following: polymers, thermoplastic polymers, polyvinyl chloride (PVC), phenolic resins, natural or synthetic rubber, synthetic wood pulp, lignin, glass fibers, synthetic fibers, cellulosic fibers, and / or combinations thereof. Natural or synthetic rubber may include rubber, latex, natural rubber, synthetic rubber, crosslinked or uncrosslinked natural or synthetic rubber, cured or uncured rubber, crumb or powdered rubber, polyisoprene, methyl rubber, polybutadiene, chloroprene rubber, butyl rubber, bromobutyl rubber, polyurethane rubber, epichlorohydrin rubber, polysulfide rubber, chlorosulfonated polyethylene, polynorbornene rubber, acrylic acid rubber, and fluororubbers such as styrene / butadiene rubber, acrylonitrile / butadiene rubber, ethylene / propylene rubber (EPM and EPDM) and ethylene / vinyl acetate rubber, as well as silicone rubber and copolymer rubbers, and / or combinations thereof.

[0036] In some embodiments of the present invention, the porous membrane composition may further contain a filler. In some embodiments, the filler is at least one of silica, dried silica powder, precipitated silica, amorphous silica, extremely brittle silica, alumina, talc, fish meal, fish bone meal, barium sulfate (BaSO4), carbon, conductive carbon, graphite, artificial graphite, activated carbon, carbon paper, acetylene black, carbon black, high surface area carbon black, graphene, high surface area graphene, Ketjenblack, carbon fiber, carbon filament, carbon nanotube, open-cell carbon foam, carbon mat, carbon felt, carbon buckminsterfullerene ("Bucky Balls"), aqueous carbon suspension, flake graphite, carbon oxide, and / or a combination thereof.

[0037] In some embodiments, the porous membrane composition may further contain process oils remaining from the manufacturing of the substrate. One advantage of the battery separators described herein is the ability to reduce the process oil content in the substrate to 20% or less, 15% or less, 10% or less, or 5% or less. For example, the process oil content can be reduced to as low as 1% or less, 2% or less, 3% or less, 4% or less, 5% or less, 6% or less, 7% or less, 8% or less, 9% or less, 10% or less, 11% or less, 12% or less, 13% or less, 14% or less, 15% or less, 16% or less, 17% or less, 18% or less, 19% or less, or 20% or less. Conventionally, a large amount of process oil was left in order to improve oxidation resistance in particular. However, by providing a material layer on at least one side of the polymer substrate in the battery separator described herein, concerns about the oxidation resistance of the substrate can be reduced, and the amount of process oil remaining in the substrate can be reduced. Reducing the amount of process oil increases the ionic conductivity of the substrate and / or the entire substrate It may have the desirable effect of reducing the electrical resistance of the body. Therefore, the ability to reduce the amount of residual process oil in the substrate leads to important and improved separator performance. It is possible. The ability to reduce the process oil content of the substrate is an advantage made possible by the improved battery separator structure described herein, but embodiments of battery separators containing more than 20% process oil in the substrate are also operable and have other advantages.

[0038] In some preferred embodiments, the porous membrane may be a porous membrane containing polyethylene. The porous membrane may be a microporous membrane. The porous membrane may be a porous polyolefin membrane, a filled polyolefin porous membrane, an absorbent glass mat (AGM), a woven fabric, a nonwoven fabric, or a combination of the above. One possible combination is an AGM with a filled polyolefin porous membrane, such as silica-filled.

[0039] In some preferred embodiments, the porous membrane is a filled polyolefin porous membrane, such as a silica-filled polyethylene product typically sold by Daramic LLC. In some preferred embodiments, the porous membrane may be an absorbent glass mat (AGM).

[0040] In some embodiments, one or more surfaces or faces of a porous membrane may have ribs, protrusions, or both ribs and protrusions. In embodiments where ribs are present, the ribs do not have any particular structure, but may be at least one of continuous ribs, discontinuous ribs, longitudinally extending ribs, transversely extending ribs, obliquely extending ribs, integral ribs, non-integrated ribs, miniribs, and combinations thereof. For example, a rib may be discontinuous and obliquely extending. A protrusion is not a rib. One example of a protrusion may include, but is not limited to, a dimple. When ribs, protrusions, or ribs and protrusions are formed on both sides of a substrate, the shapes of the ribs, protrusions, or ribs and protrusions formed on each surface or face of the substrate may be identical or different. For example, transversely extending ribs may be formed on one surface or face of the substrate, and longitudinally extending ribs may be formed on the other surface or face. In some preferred embodiments, transversely extending ribs may be formed on the positive electrode surface of the porous membrane, and longitudinally extending ribs may be formed on the negative electrode surface (i.e., negative electrode side crossing ribs).

[0041] In some embodiments in which ribs, protrusions, or ribs and protrusions are formed on the surface of the substrate, one or more edge regions of the substrate may not contain ribs, protrusions, or ribs and protrusions, and one or more edge regions may contain only miniribs, miniprotrusions, or miniribs and protrusions. The miniribs or miniprotrusions may have a maximum height of 100 to 250 microns from the substrate surface to the highest point of the rib or protrusion. In some embodiments, the maximum height may be up to 75 microns, up to 50 microns, up to 25 microns, up to 125 microns, up to 150 microns, up to 175 microns, up to 200 microns, or up to 225 microns. This type of structure may be useful when the final structure of the battery separator is a pouch or sleeve that requires to be formed by welding the edges of the substrate material. In such embodiments in which regions without ribs or protrusions (or with only miniribs or protrusions) are formed, it is preferable that no material layer is formed in these regions either.

[0042] In some embodiments, the thickness of the substrate may be in the range of 50-500 microns, 75-500 microns, 100-500 microns, 125-500 microns, 150-500 microns, 175-500 microns, 200-500 microns, 225-500 microns, 250-500 microns, 300-500 microns, 325-500 microns, 350-500 microns, 375-500 microns, 400-500 microns, 425-500 microns, 450-500 microns, or 475-500 microns.

[0043] Surfactant coating The surfactant coating includes nonionic surfactants and ionic surfactants. In some preferred embodiments, the basis weight of the nonionic surfactant on the porous film is 10 g / m². 2 Below, 9g / m 2 Below, 8g / m 2 Below, 7g / m 2 Below 6g / m 2 Below, 5g / m 2 Below, 4g / m 2 Below 3g / m2 Below, 2g / m 2 The following, or 1 g / m² 2 The following applies: In some preferred embodiments, the basis weight of the nonionic surfactant is 1 g / m². 2 ~5g / m 2 , 1g / m 2 ~4g / m 2 , 1g / m 2 ~3g / m 2 , 2g / m 2 ~4g / m 2 2.5g / m 2 ~4g / m 2 , or 3g / m 2 ~4g / m 2 The ionic surfactant is found in concentrations of 0.5 wt% to 5.0 wt%, 0.5 wt% to 4.0 wt%, 0.5 wt% to 3.0 wt%, and 1.0 wt% to 4.0 wt%, based on the weight of the separator. It may be present on the porous membrane in amounts of 1.0 wt% to 3.0 wt%, or 1.0 wt% to 2.0 wt%.

[0044] Nonionic surfactants are not particularly limited. Examples include: aliphatic alcohols, cetyl alcohol, stearyl alcohol, pentaethylene glycol monododecyl ether, polyoxypropylene glycol alkyl ether, polyoxyethylene glycol, octylphenol ether, polyoxyethylene glycol alkyl ether, octaethylene glycol monododecyl ether, polyoxyethylene glycol alkylphenol ether, polyoxyethylene glycol sorbitan alkyl ester, oleyl alcohol, polyethylene glycol block copolymer, polypropylene glycol block copolymer, glucoside alkyl ether, decyl glucoside, lauryl glucoside, octyl glucoside, nonoxynol-9, glycerol alkyl ester, polysorbate, sorbitan alkyl ester, laurate This may be at least one selected from lyceryl, cocamide, costearyl alcohol, metharyl-capped nonionic surfactant, polyol fatty acid ester, polyethoxylate ester, polyethoxylate aliphatic alcohol, alkyl polysaccharide, alkyl polyglucoside, amine ethoxylate, sorbitan fatty acid ester ethoxylate, organosilicone surfactant, ethylene vinyl acetate terpolymer, ethoxylate alkylaryl phosphate ester, sucrose fatty acid ester, polyethoxylate alcohol, polyethylene oxide, acid-soluble sugar, sucrose fatty acid ester, organic fatty acid, hydroxyl acid, nonionic surfactant, octylphenol ethoxylate surfactant, octylphenol ethoxylate nonionic surfactant, and combinations thereof.

[0045] In some embodiments, the nonionic surfactant is a nonionic surfactant having a cloud point greater than about 15°C, greater than about 20°C, or greater than about 25°C.

[0046] In some embodiments, the nonionic surfactant may have a structure with the following chemical formula.

[0047] [ka]

[0048] In the structure described above, n may be an integer between 5 and 20, 6 and 20, 7 and 20, 8 and 20, 9 and 20, 10 and 20, 11 and 20, 12 and 20, 13 and 20, 14 and 20, 15 and 20, 16 and 20, 17 and 20, 18 and 20, 19 and 20, or between 9 and 17; m may be an integer between 1 and 15, 2 and 15, 3 and 15, 4 and 15, 5 and 15, 6 and 15, 7 and 15, 8 and 15, 9 and 15, 10 and 15, 11 and 15, 12 and 15, 13 and 15, 14 and 15, or between 6 and 10; and p may be an integer between 0 and 10, 0 and 9, 0 and 8, 0 and 7, 0 and 6, or 0 The integer can be between 5, 0-4, 0-3, 0-2, 0-1, or 0-7.

[0049] The ionic surfactant may be a cationic surfactant, an anionic surfactant, or an amphoteric surfactant.

[0050] In some embodiments, the ionic surfactant is sulfate, alkyl sulfate, ammonium lauryl sulfate, sodium lauryl sulfate, alkyl ether sulfate, sodium laureth sulfate, sulfonate, docusate, sodium dioctyl sulfosuccinate, alkylbenzene sulfonic acid, phosphate, alkyl ether phosphate, carboxylate, alkyl carboxylate, fatty acid salt, sodium stearate, sodium lauroyl sarcosinate, alkyltrimethylammonium, cetylpyridinium, polyethoxylated taluamine, benzalkonium, benzethonium, dimethyldioctadecylammonium The sulfosuccinate may be at least one selected from dioctadecyldimethylammonium salts of alkylsulfonic acids, alkylarylsulfonates, alkylphenol-alkylene oxide addition products, soaps, alkyl-naphthalene-sulfonates, anionic sulfosuccinates, dialkyl esters of sulfosuccinates, amine compounds (primary, secondary, tertiary, or quaternary amines), block copolymers of ethylene oxide and propylene oxide, various polyethylene oxides, mono and dialkyl phosphate ester salts, and mixtures thereof.

[0051] In some embodiments, the ionic surfactant may be an anionic surfactant having the following chemical formula structure.

[0052] [ka]

[0053] In the above formula, n is an integer between 0 and 10, 0 and 9, 0 and 8, 0 and 7, 0 and 6, 0 and 5, 0 and 4, 0 and 3, 0 and 2, or 0 and 1; m is an integer between 0 and 10, 0 and 9, 0 and 8, 0 and 7, 0 and 6, 0 and 5, 0 and 4, 0 and 3, 0 and 2, or 0 and 1; and R1 is a linear chain of H, C1 and C10, C1 and C9, C1 and C8, C1 and C7, C1 and C6, C1 and C5, C1 and C4, C1 and C3, or C1 and C2. Alternatively, it may be a branched saturated or unsaturated alkyl group, an aliphatic alcohol of C1-C10, C1-C9, C1-C8, C1-C7, C1-C6, C1-C5, C1-C4, C1-C3, or C1-C2, an alcohol of C1-C10, C1-C9, C1-C8, C1-C7, C1-C6, C1-C5, C1-C4, C1-C3, or C1-C2, or an aromatic group, and R2 is H, C1-C 10. Straight-chain or branched saturated or unsaturated alkyl groups of C1-C9, C1-C8, C1-C7, C1-C6, C1-C5, C1-C4, C1-C3, or C1-C2; straight-chain or branched saturated or unsaturated aliphatic alcohols of C1-C10, C1-C9, C1-C8, C1-C7, C1-C6, C1-C5, C1-C4, C1-C3, or C1-C2; C1-C10, C1-C9 , C1-C8, C1-C7, C1-C6, C1-C5, C1-C4, C1-C3, or C1-C2 linear or branched saturated or unsaturated alcohol or aromatic group, n and m are the same or different, R1 and R2 are the same or different, R3 is hydrogen or a methyl group, R4 is hydrogen or a methyl group, R3 and R4 are the same or different, and X is SO3 - COO - , PO4 -2 , and similar negatively charged groups. Positively charged counterions for anionic surfactants also exist, such as Na + , K + Li + NH4 + Ca 2+ Mg 2+ , and at least one of the same.

[0054] In some embodiments, the ionic surfactant may be an anionic surfactant having the following chemical formula structure.

[0055] [ka]

[0056] In another embodiment, a battery separator described herein may exhibit at least one of the following: a perox80 value of 90% or more, 91% or more, 92% or more, 93% or more, 94% or more, 95% or more, 96% or more, 97% or more, 98% or more, 99% or more, or 100% of the initial value before the perox80 test, and an ERBOIL value of less than 60, less than 50, less than 40, less than 30, less than 20, less than 10, or less than 5 or less than 1.

[0057] lead acid battery In another embodiment, 1) a lead-acid battery comprising the battery separator described herein and at least one grid comprising lead or a lead alloy, wherein the grid exhibits reduced grid corrosion compared to a battery comprising a battery separator not disclosed herein, i.e., a battery separator on which the surfactant blend described herein is not applied. In the ERBOIL test, the separator is exposed to boiling water for 10 minutes, then immersed in sulfuric acid for 20 minutes. After this, the electrical resistance (ER) is measured.

[0058] In another embodiment, a lead-acid battery is described as comprising a battery separator as described herein, wherein the battery has a black residue rate of less than 3, less than 2, or less than 1.

[0059] In another embodiment, a lead-acid battery is described in which the lead-acid battery includes a battery separator described herein, and the battery exhibits improved partially charged state (PSOC) cycle life test results. The PSOC cycle life test results are compared to those of a battery having a separator that does not contain the surfactant blend described herein.

[0060] Battery separator 2 In another embodiment, a battery separator comprising a porous membrane and a surfactant coating containing a nonionic surfactant on at least one side of the porous membrane, wherein the basis weight of the nonionic surfactant coating is 1 g / m² 2 ~5g / m 2 A battery separator is described herein. The basis weight of the nonionic surfactant coating is 2 g / m². 2 ~4g / m 2 , or 3g / m 2 ~4g / m 2 This may also apply. The surfactant coating may also include the ionic surfactants described herein. A battery containing this battery separator may exhibit at least one of the following compared to a battery containing a separator with a high concentration of nonionic surfactant coating: longer discharge life, less water loss, improved charge acceptance, and longer lifespan.

[0061] Battery separator 3 In another embodiment, a battery separator comprising a porous membrane and a surfactant coating is described. In this embodiment, the surfactant of the surfactant coating comprises, or substantially comprises, a compound having the structure of the following chemical formula:

[0062] [ka]

[0063] In the above chemical formula, n is an integer between 0 and 10, 0 and 9, 0 and 8, 0 and 7, 0 and 6, 0 and 5, 0 and 4, 0 and 3, 0 and 2, or 0 and 1, and m is an integer between 0 and 10, 0 and 9, 0 and 8, 0 and 7, 0 and 6, 0 and 5, 0 and 4, 0 and 3, 0 and 2, or 0 and 1, and n and m may be the same or different, and R1 is a linear or Branched saturated or unsaturated alkyl groups, C1-C10, C1-C9, C1-C8, C1-C7, C1-C6, C1-C5, C1-C4, C1-C3, or C1-C2 aliphatic alcohols, C1-C10, C1-C9, C1-C8, C1-C7, C1-C6, C1-C5, C1-C4, C1-C3, or C1-C2 alcohols, or aromatic groups, where R2 is H, C1-C10, C1-C9, C1-C8, C1-C7, C1-C6, C1 Straight-chain or branched saturated or unsaturated alkyl groups of ~C5, C1~C4, C1~C3, or C1~C2; straight-chain or branched saturated or unsaturated aliphatic alcohols of C1~C10, C1~C9, C1~C8, C1~C7, C1~C6, C1~C5, C1~C4, C1~C3, or C1~C2; straight-chain or branched alkyl groups of ~C5, C1~C4, C1~C3, or C1~C2. The branch is a saturated or unsaturated alcohol or aromatic group, where n and m are the same or different, R1 and R2 are the same or different, R3 is hydrogen, a methyl group, or a C1-C5, C1-C4, C1-C3, or C1-C2 alkyl group, R4 is hydrogen, a methyl group, or a C1-C5, C1-C4, C1-C3, or C1-C2 alkyl group, where R3 and R4 are the same or different, and X is SO3 - COO - , PO4 - , and similar negatively charged groups, or positively charged counterions. In some embodiments, R3 and R4 are identical and both are hydrogen. In some embodiments, R3 and R4 are identical and both are methyl groups. In some embodiments, X is SO3 -In some embodiments, X is the COO - In some embodiments, X is PO4 -2 In some embodiments, m and n are integers between 1 and 5, 1 and 4, 1 and 3, or 1 and 2, or integers between 6 and 10, 6 and 9, 6 and 8, or 6 and 7, respectively. In some embodiments, n is an integer between 1 and 5, 1 and 4, 1 and 3, or 1 and 2, or integers between 6 and 10, 6 and 9, 6 and 8, or 6 and 7. In some embodiments, m is an integer between 1 and 5, 1 and 4, 1 and 3, or 1 and 2, or integers between 6 and 10, 6 and 9, 6 and 8, or 6 and 7. In some embodiments, q is an integer between 1 and 10, 1 and 9, 1 and 8, 1 and 7, 1 and 6, 1 and 5, 1 and 4, 1 and 3, or 1 and 2, or integers between 6 and 10, 6 and 9, 6 and 8, or 6 and 7. In some embodiments, r is an integer between 1 and 10, 1 and 9, 1 and 8, 1 and 7, 1 and 6, 1 and 5, 1 and 4, 1 and 3, or 1 and 2, or an integer between 6 and 10, 6 and 9, 6 and 8, or 6 and 7. In some embodiments, s is an integer between 1 and 10, 1 and 9, 1 and 8, 1 and 7, 1 and 6, 1 and 5, 1 and 4, 1 and 3, or 1 and 2, or an integer between 6 and 10, 6 and 9, 6 and 8, or 6 and 7. In some embodiments, the surfactant has the following chemical formula structure.

[0064] [ka]

[0065] The examples were prepared using nonionic surfactants having PPO and PEO blocks, such as those represented by one of the following chemical formulas.

[0066] [ka]

[0067] In the above formula, n may be an integer between 12 and 15, m may be an integer between 1 and 15 or between 6 and 10, and p may be an integer between 0 and 10 or between 0 and 7. Low, medium, and high amounts of surfactant were applied to the same type of Daramic® separator. These examples were evaluated. Comparative examples using the same type of Daramic® separator but without the use of a nonionic surfactant were also evaluated. The evaluation results are shown in Table 1 below.

[0068] [Table 1]

[0069] Therefore, the inventors found that the use or addition of a low amount of nonionic surfactant resulted in unexpectedly improved battery characteristics compared to the comparative examples and the examples with medium and high amounts of surfactant. The low amount of nonionic surfactant was 5 g / m². 2 Smaller, and 1 g / m² 2 It is thought to be larger, but 2g / m 2 ~4g / m 2 or 3g / m 2 ~4g / m 2 These improved characteristics include higher partial charge state cycles, improved charge acceptance, and lower water loss.

[0070] The examples were prepared using a blend of a nonionic surfactant and an anionic surfactant having the following chemical formula structure.

[0071] [ka]

[0072] For the comparative examples, only nonionic surfactants were used. In each example, the surfactant or surfactant blend was coated onto the same Daramic® separator. These examples are shown in Table 2.

[0073] [Table 2]

[0074] The addition of anionic surfactants to nonionic surfactants was found to reduce the black residue rate, as shown in Figure 1. Reducing black residue is important because it can improve battery safety by enhancing the ability to properly maintain the battery. If black residue increases excessively within the battery, this residue can clog the "magic eye," which is a part of the battery that notifies the operator when maintenance is needed. We also found that the addition of approximately 1% anionic surfactant was necessary to obtain the aforementioned favorable results.

[0075] The addition of anionic surfactants is also useful in preventing lattice corrosion. This is shown in Figure 2, where the lattice on the left was found in a battery equipped with a separator like that in Comparative Example B, and the lattice on the right was found in a battery equipped with a separator like that in Example 4 or 5.

[0076] As shown in the graph in Figure 3, the plates used in batteries with separators such as those in Example 4 or 5 showed a 13.5% reduction in grid weight loss at the end of life (@12 weeks J280).

[0077] Examples 6 and 7 are formed including a surfactant coating on a Daramic® separator. Each surfactant coating consists of one surfactant having one of the following chemical formula structures, or two or more surfactants each having one of the following chemical formula structures.

[0078] [ka]

[0079] In the above chemical formula, n is an integer from 0 to 10, m is an integer from 0 to 10, n and m can be the same or different, R1 is H, a linear or branched saturated or unsaturated alkyl group with 1 to 10 carbon atoms, an aliphatic alcohol with 1 to 10 carbon atoms, an alcohol with 1 to 10 carbon atoms, or an aromatic group, R2 is H, a linear or branched saturated or unsaturated alkyl group with 1 to 10 carbon atoms, a linear or branched saturated or unsaturated aliphatic alcohol with 1 to 10 carbon atoms, a linear or branched saturated or unsaturated alcohol with 1 to 10 carbon atoms, or an aromatic group, n and m can be the same or different, R1 and R2 can be the same or different, R3 is hydrogen or a methyl group or an alkyl group with 1 to 5 carbon atoms, R4 is hydrogen or a methyl group or an alkyl group with 1 to 5 carbon atoms, R3 and R4 can be the same or different, and X is SO3 - , COO - , PO4 -2 , and similar negatively charged groups, or is also a positively charged counter ion. In some embodiments, R3 and R4 are the same and both are hydrogen. In some embodiments, R3 and R4 are the same and both are methyl groups. In some embodiments, X is SO3 - . In some embodiments, X is COO - . In some embodiments, X is PO4 -2 . In some embodiments, m and n are each an integer from 1 to 5, or each an integer from 6 to 10. In some embodiments, n is an integer from 1 to 5 or an integer from 6 to 10. In some embodiments, m is an integer from 1 to 5 or an integer from 6 to 10. In some embodiments, q is an integer from 1 to 10, 1 to 5 or 6 to 10, r is an integer from 1 to 10, 1 to 5 or 6 to 10. In some embodiments, s is an integer from 1 to 10, 1 to 5 or 6 to 10.

Claims

1. Porous membrane and A surfactant on at least one side of the porous membrane, A battery separator including, A battery separator wherein the surfactant comprises a mixture of at least one ionic surfactant and at least one nonionic surfactant.

2. The at least one nonionic surfactant is an aliphatic alcohol, cetyl alcohol, stearyl alcohol, pentaethylene glycol monododecyl ether, polyoxypropylene glycol alkyl ether, polyoxyethylene glycol, octylphenol ether, polyoxyethylene glycol alkyl ether, octaethylene glycol monododecyl ether, polyethylene glycol alkylphenol ether, polyoxyethylene glycol sorbitan alkyl ester, oleyl alcohol, polyethylene glycol block copolymer, polypropylene glycol block copolymer, glucoside alkyl ether, decyl glucoside, lauryl glucoside, octyl glucoside, nonoxynol-9, glycerol alkyl ester, polysorbate, sorbitan alkyl ester, laurin A battery separator according to claim 1, comprising at least one selected from glyceryl acid, cocamide, costearyl alcohol, metharyl-capped nonionic surfactant, polyol fatty acid ester, polyethoxylate ester, polyethoxylate aliphatic alcohol, alkyl polysaccharide, alkyl polyglucoside, amine ethoxylate, sorbitan fatty acid ester ethoxylate, organosilicone surfactant, ethylene vinyl acetate terpolymer, ethoxylate alkylaryl phosphate ester, sucrose fatty acid ester, polyethoxylate alcohol, polyethylene oxide, acid-soluble sugar, sucrose fatty acid ester, organic fatty acid, hydroxyl acid, nonionic surfactant, octylphenol ethoxylate surfactant, octylphenol ethoxylate nonionic surfactant, and combinations thereof.

3. The battery separator according to claim 1, wherein the nonionic surfactant has a cloud point greater than 15°C, greater than 20°C, or greater than 25°C.

4. The battery separator comprises at least one nonionic surfactant having a molecule with the following chemical formula structure, The battery separator according to claim 1, wherein n is an integer between 5 and 20 or between 9 and 17, m is an integer between 1 and 15 or between 6 and 10, and p is an integer between 0 and 10 or between 0 and 7. 【Chemistry 1】

5. The battery separator according to claim 1, wherein the at least one ionic surfactant is an anionic surfactant.

6. The battery separator according to claim 1, wherein the ionic surfactant is a cationic surfactant selected from ammonium alkoxylated salts.

7. The battery separator according to claim 1, wherein the at least one ionic surfactant is an amphoteric surfactant selected from alkoxylated amino acids.

8. The aforementioned ionic surfactants include sulfates, alkyl sulfates, ammonium lauryl sulfate, sodium lauryl sulfate, alkyl ether sulfates, sodium laureth sulfate, sulfonates, docusate, sodium dioctyl sulfosuccinate, alkylbenzene sulfonic acid, phosphates, alkyl ether phosphates, carboxylates, alkyl carboxylates, fatty acid salts, sodium stearate, sodium lauroyl sarcosinate, alkyltrimethylammonium, cetylpyridinium, polyethoxylated taloamine, benzalkonium, benzethonium, dimethyldioctadecylammonium, and alkyl sulfonic acid. A battery separator according to claim 1, comprising at least one selected from octadecyldimethylammonium salt, alkylaryl sulfonate, alkylphenol-alkylene oxide addition product, soap, alkyl-naphthalene-sulfonate, anionic sulfosuccinate, one or more sulfosuccinates, dialkyl esters of sulfosuccinates, amine compounds (primary, secondary, tertiary, or quaternary amines), block copolymers of ethylene oxide and propylene oxide, various polyethylene oxides, mono and dialkyl phosphate ester salts, and mixtures thereof.

9. The ionic surfactant is a battery separator having a structure of any of the following chemical formulas, In the following formula, n is an integer from 0 to 10, m is an integer from 0 to 10, n and m are the same or different, q is an integer from 0 to 10, r is an integer from 0 to 10, s is an integer from 0 to 10, and q, r and s are the same or different, R1 is H, a linear or branched saturated or unsaturated alkyl group of C1 to C10, an aliphatic alcohol of C1 to C10, an alcohol of C1 to C10, or an aromatic group, and R2 is H, a linear or branched saturated alkyl group of C1 to C10 Alternatively, it is an unsaturated alkyl group, a C1-C10 linear or branched saturated or unsaturated aliphatic alcohol, a C1-C10 linear or branched saturated or unsaturated alcohol, or an aromatic group, where n and m are the same or different, R1 and R2 are the same or different, R3 is hydrogen, a methyl group, or a C1-C5 alkyl group, R4 is hydrogen, a methyl group, or a C1-C5 alkyl group, where R3 and R4 are the same or different, and X is SO ３ － COO － , PO ４ －２ The battery separator according to claim 1, which is a negatively charged group or a positively charged counterion of the same type. 【Chemistry 2】

10. The ionic surfactant has a structure with the following chemical formula, comprising a positively charged counterion, wherein the counterion is selectively Na ＋ The battery separator according to claim 1. 【Transformation 3】

11. The battery separator according to claim 1, wherein 0.5 to 5.0 wt% of the ionic surfactant is added.

12. The battery separator according to claim 11, wherein 1.0 to 3.0 wt% of the ionic surfactant is added.

13. The basis weight of the nonionic surfactant is 10 g / m². ２ A battery separator according to claim 1, wherein the value is less than [value missing].

14. The basis weight of the aforementioned nonionic surfactant is 7 g / m². ２ A battery separator according to claim 13, wherein the value is less than [value missing].

15. The basis weight of the nonionic surfactant is 1 g / m ２ to 5 g / m ２ , 1 g / m ２ to 4 g / m ２ , or 2.5 g / m ２ to 4 g / m ２ ; the battery separator according to claim 13

16. The battery separator according to claim 1, wherein the porous membrane is a porous membrane containing polyethylene.

17. The battery separator according to claim 1, wherein the battery separator exhibits at least one of the following conditions: the perox80 value is 90% or more, 91% or more, 92% or more, 93% or more, 94% or more, 95% or more, 96% or more, 97% or more, 98% or more, 99% or more, or 100% of the initial value before the perox80 test, and the ERBOIL value is less than 60.

18. A battery separator according to claim 1, A grid containing lead or a lead alloy, A lead-acid battery that includes, A lead-acid battery exhibiting reduced grid corrosion compared to the same battery having the separator comprising a coating containing a nonionic surfactant but not an ionic surfactant.

19. A lead-acid battery comprising a battery separator according to claim 1, wherein the battery has a black residue rate of less than 3.

20. The lead-acid battery according to claim 19, wherein the black residue rate is less than 2.

21. A lead-acid battery comprising a battery separator according to claim 1, wherein the battery exhibits a PSOC (partially charged) cycle life of more than 10,000 cycles, more than 20,000 cycles, more than 30,000 cycles, more than 40,000 cycles, or more than 45,000 cycles.

22. Porous membrane and A surfactant containing a nonionic surfactant is provided on at least one side of the porous membrane, A battery separator including, The basis weight of the nonionic surfactant is 1 g / m². ２ ~5g / m ２ This is a battery separator.

23. The basis weight of the nonionic surfactant is 2 g / m². ２ ~4g / m ２ The battery separator according to claim 22.

24. The basis weight of the nonionic surfactant is 3 g / m². ２ ~4g / m ２ As described in claim 23. Battery separator.

25. A lead-acid battery comprising the battery separator according to claim 22, wherein the battery exhibits at least one of a longer discharge life, less water loss, improved charge acceptance, a longer partially charged cycle life, and a longer lifespan compared to a separator comprising a high concentration of nonionic surfactant.

26. Porous membrane and Surfactants and Includes, The surfactant is a compound having a structure of any of the following chemical formulas, In the following formula, n is an integer from 0 to 10, m is an integer from 0 to 10, n and m are the same or different, q is an integer from 0 to 10, r is an integer from 0 to 10, s is an integer from 0 to 10, and q, r and s are the same or different, R1 is H, a linear or branched saturated or unsaturated alkyl group of C1 to C10, an aliphatic alcohol of C1 to C10, an alcohol of C1 to C10, or an aromatic group, and R2 is H, a linear or branched saturated or unsaturated alkyl group of C1 to C10. k is an unsaturated alkyl group, a C1-C10 linear or branched saturated or unsaturated aliphatic alcohol, a C1-C10 linear or branched saturated or unsaturated alcohol, or an aromatic group, n and m are the same or different, R1 and R2 are the same or different, R3 is hydrogen, a methyl group, or a C1-C5 alkyl group, R4 is hydrogen, a methyl group, or a C1-C5 alkyl group, R3 and R4 are the same or different, and X is SO ３ － COO － , PO ４ －２ A battery separator that is a negatively charged group or a positively charged counterion, and similar negatively charged groups. 【Chemistry 4】

27. R3 and R4 are identical and both are hydrogen atoms, R3 and R4 are identical and both are methyl groups, X is SO ３ － Is X PO ４ －２ The battery separator according to claim 26, wherein m and n are both integers from 1 to 5, m and n are both integers from 6 to 10, m is an integer from 1 to 5, n is an integer from 1 to 5, m is an integer from 6 to 10, n is an integer from 6 to 10, q, r and s are each integers from 1 to 5, q, r and s are each integers from 6 to 10, q is an integer from 1 to 5, r is an integer from 1 to 5, s is an integer from 1 to 5, q is an integer from 6 to 10, r is an integer from 6 to 10, or s is an integer from 6 to 10.

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