WO2025106476A1 - Séparateurs de batterie à tailles de pores réduites - Google Patents

Séparateurs de batterie à tailles de pores réduites Download PDF

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Publication number
WO2025106476A1
WO2025106476A1 PCT/US2024/055626 US2024055626W WO2025106476A1 WO 2025106476 A1 WO2025106476 A1 WO 2025106476A1 US 2024055626 W US2024055626 W US 2024055626W WO 2025106476 A1 WO2025106476 A1 WO 2025106476A1
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Prior art keywords
layer
weight
battery separator
separator
pva
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PCT/US2024/055626
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English (en)
Inventor
Axel LE NOZAHIC
Christelle BELLOUARD
Oxana CHERKAS
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Swm Holdco Luxembourg SARL
Swm Holdings Us LLC
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Swm Holdco Luxembourg SARL
Swm Holdings Us LLC
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Publication of WO2025106476A1 publication Critical patent/WO2025106476A1/fr
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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/429—Natural polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/429—Natural polymers
    • H01M50/4295—Natural cotton, cellulose or wood
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/30—Nickel accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/04—Cells with aqueous electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • This description generally relates to primary and secondary batteries, battery separators and methods of making such separators and more particularly to a battery separator having a reduced pore size.
  • Separator papers for primary and secondary batteries serve as a mechanical barrier between the electrodes to prevent shorting while allowing for ionic transport through the electrolyte in the pores.
  • Separators should have good mechanical integrity, chemical inertness, well-defined and consistent porosity and tortuosity in order to uniformly transport the ions between the electrodes.
  • Separator papers used in such batteries often comprise blends of polyvinyl alcohol (PVA) fibers and cellulose, such as dissolving pulp, rayon or lyocell.
  • PVA polyvinyl alcohol
  • separators made from fibers may be designed at various levels of basis weight.
  • the availability of low count PVA, as well as rayon fibers, has enabled a trend toward lighter material, targeting space savings in the cells to permit higher amounts of active material and enhance discharge performance.
  • the use of fibers in the manufacturing of battery separators also contributes significantly to reduced costs as compared to more traditional polyolefin materials.
  • battery separators made from fibers allow for reduced pore sizes to help control the generation of dendrites which may hinder performance, or in some cases, cause short circuits. Reduced pore size also allows for battery separators to better block the penetration of active components of the electrode materials and any conductive additives.
  • Batteries and battery separators are provided for use in a variety of different batteries, including, but not limited to, primary, secondary and/or stationary batteries, such as zincmanganese dioxide (Zn/MnCh), nickel-cadmium (Ni-Cd,), lithium-ion (Li-ion), nickel-hydrogen (Ni-H 2 ) batteries and the like.
  • primary, secondary and/or stationary batteries such as zincmanganese dioxide (Zn/MnCh), nickel-cadmium (Ni-Cd,), lithium-ion (Li-ion), nickel-hydrogen (Ni-H 2 ) batteries and the like.
  • a two-layer alkaline battery separator comprises a first base layer of about 20% to about 50% by weight polyvinyl alcohol (PVA) and about 50% to about 80% by weight cellulose based on the total dry weight of the first base layer, and a second layer in contact with a surface of the first base layer.
  • the second layer comprises PVA and a polysaccharide.
  • the separator has a maximum pore size of less than about 2.0 ⁇ m.
  • the second layer comprises a coating adhered to a surface of the base layer. Applying the coating to the base layer further tightens the pore size, while keeping the wet ionic resistance or electrical resistance (also referred to as ionic resistivity and measured according to ASTM Test E7148-19 (2019)) from increasing to undesirable ranges.
  • the base layer essentially functions as a ground layer that provides liquid absorption properties and a relatively tight pore structure, while the coating functions as a finishing layer that further tightens the porous structure and provides improved short circuit shielding.
  • providing only two layers for the battery separator facilitates manufacturing and reduces the overall cost of the separator.
  • the separator consists of only the base layer and the coating.
  • the coating has a relatively low basis weight compared to the base layer to mitigate the increase in ionic resistance across the separator.
  • the ratio of the basis weight of the base layer to the coating layer may be about 2 to about 12, such as from about 2 to about 5 or from about 5 to about 8.
  • the maximum pore size of the separator is less than about 1.8 ⁇ m or about 1.6 ⁇ m or less.
  • the mean pore size of the separator is less than about 1.0 ⁇ m or about 0.7 ⁇ m or less.
  • the difference between the maximum pore size and the mean pore size of the separator is less than about 2.0 ⁇ m, or less than about 1.0 ⁇ m. Minimizing the difference between the maximum and mean pores sizes (i.e., the pore size distribution) of the separator improves the overall performance of the battery.
  • the base layer comprises a blend of polyvinyl alcohol and one of lyocell fibers, viscose fibers, dissolving pulp, mercerized pulp or a combination thereof.
  • the base layer may include PVA in a percentage by dry weight of about 20% to about 50%, or about 35% to about 45%.
  • the PVA is present in the first layer in about 40% by dry weight.
  • the cellulose may be present in a percentage by dry weight of about 50% to about 80% of the first layer, or about 55% to about 65%.
  • the cellulose comprises lyocell fibers and can be present in an amount of about 60% of the base layer based on the total dry weight of base layer.
  • the PVA in the first layer comprises non-soluble PVA fibers and a water soluble PVA binder.
  • the PVA binder is generated by water soluble PVA fibers that change shape as water evaporates from the separator.
  • the first layer comprises about 20% to about 30% by dry weight non-soluble PVA fibers, or about 25% by dry weight non-soluble PVA fibers, and about 10% to about 20% by dry weight water soluble PVA binder, or about 15% by dry weight water soluble PVA binder.
  • the non-soluble PVA fibers have a linear density greater than about 0.3 denier, or about 0.4 to about 0.6 denier, or about 0.5 denier. In other embodiments, the linear density is about 1.0 denier.
  • the polysaccharide in the second coating layer comprises a material selected from cellulose fibers, cellulose nanofilaments, microcrystalline cellulose, microcrystalline cellulose gel, starch, carboxymethyl cellulose (CMC), hydroxypropyl methylcellulose (HPMC), alginate, micro fibrillated cellulosic fibers, or combinations thereof.
  • the coating comprises microcrystalline cellulose or microcrystalline cellulose gel in a percentage by dry weight of at least about 20%, or at least about 40% of the coating layer.
  • the gel is present in a percentage by weight of about 50% of the coating layer based on the total dry weight of coating.
  • the coating layer further comprises PVA, such as a high molecular weight PVA resin, or a water soluble PVA resin.
  • PVA such as a high molecular weight PVA resin, or a water soluble PVA resin.
  • the second layer comprises PVA in a percentage by dry weight of at least about 20%, or at least about 40% of the coating layer.
  • the PVA is present in a percentage by dry weight of about 50% of the coating layer.
  • the ionic resistance of the separator is less than about 100 mOhm-cm 2 , or less than about 95 mOhm-cm 2 , or less than about 90 mOhm-cm 2 , or less than about 80 mOhm-cm 2 , or less than about 60 mOhm-cm 2 .
  • the KOH absorption of the separator may be at least about 80 g/m 2 , or from about 80 g/m 2 to about 200 g/m 2 or about 100 g/m 2 to about 130 g/m 2 .
  • the Gurley Air Resistance of the separator is at least about 500 sec/lOOml, or at least about 750 sec/lOOml, or at least about 1,000 sec/lOOml, or at least about 1,450 sec/lOOml. This relatively high air resistance reduces the amount of air that passes through the separator, which improves the overall performance of the battery.
  • a battery comprising the separator described above.
  • the battery may comprise a primary or a secondary battery, which may comprise a stationary battery.
  • the battery comprises a zinc-manganese dioxide (Zn/MnCh), a nickel- cadmium (Ni-Cd,), a lithium-ion (Li-ion) or a nickel-hydrogen (N1-H2) battery.
  • a battery separator consists of a first layer of about 20% to about 50% by dry weight of polyvinyl alcohol (PVA) and about 50% to about 80% by dry weight cellulose and a coating in contact with a surface of the first layer.
  • the coating comprises PVA and a polysaccharide.
  • the ratio of basis weight of the first layer to the coating is about 2 to about 12.
  • the ratio of basis weight of the first layer to the coating is about 2 to about 5, or about 5 to about 8.
  • the maximum pore size of the separator is less than about 2.0 ⁇ m, or less than about 1.8 ⁇ m or about 1.6 ⁇ m or less.
  • the mean pore size of the separator is less than about 1.0 ⁇ m or about 0.7 ⁇ m or less.
  • the difference between the maximum pore size and the mean pore size of the separator is less than about 2.0 ⁇ m, or less than about 1.0 ⁇ m.
  • the first layer comprises PVA in about 40% by weight and lyocell fibers in about 60% by weight based on the total dry weight of the first layer.
  • the PVA may comprise both non-soluble PVA fibers and a water soluble PVA binder.
  • the second layer comprises microcrystalline cellulose gel in a percentage by dry weight of about 50% and PVA, such as high molecular weight PVA resin, in a percentage by dry weight of about 50% of the coating layer.
  • a battery comprising the separator described above.
  • the battery may comprise a primary or a secondary battery, such as a stationary battery.
  • the battery comprises a zinc-manganese dioxide (Zn/MnCh), nickel-cadmium (Ni- Cd,), lithium-ion (Li-ion) or nickel-hydrogen (Ni-IL) battery.
  • an alkaline battery separator comprises a first layer of about 20% to about 50% by dry weight of polyvinyl alcohol (PVA) and about 50% to about 80% by dry weight cellulose, and a second layer of PVA and a polysaccharide in contact with a surface of the first layer.
  • PVA polyvinyl alcohol
  • the difference between a maximum pore size and a mean pore size of the separator is less than about 2.0 ⁇ m, or less than about 1.0 ⁇ m.
  • a ratio of the maximum pore size to the mean pore size of the separator is about 1.0 to about 4.0 or about 1.5 to about 2.5.
  • the maximum pore size may be less than about 300% of the mean pore size or less than about 250%.
  • the separator consists of only the first base layer and the second layer.
  • the ratio of basis weight of the first layer to the second layer may be about 2 to about 12, or about 2 to about 5, or about 5 to about 8.
  • a battery comprising the separator described above.
  • FIG. 1 is a cross-sectional view of an alkaline battery
  • FIG. 2A illustrates a cylindrical secondary battery
  • FIG. 2B illustrates a flat jelly roll secondary battery
  • FIG. 2C illustrates a stack of unit cells in a secondary battery
  • FIG. 3 A is a side view of a single sheet stacking arrangement for a secondary battery
  • FIG. 3B is a side view of a Z-stacking arrangement for a secondary battery
  • FIG. 3C is a side view of a cylindrical winding stacking arrangement for a secondary battery
  • FIG. 3D is a side view of a prismatic winding stacking arrangement for a secondary battery.
  • FIG. 4 is a cross-sectional view of a battery separator for an alkaline battery
  • the battery separators have reduced pore sizes to control the generation of dendrites and block the penetration of active components of the electrode materials and any conductive additives, while still maintaining desirable wet ionic resistance, thickness and absorption performance properties.
  • the separators can be used in various batteries, including, but not limited to, primary and secondary batteries, such as stationary batteries, zinc-manganese dioxide (Zn/MnCh), nickel-cadmium (Ni-Cd,), lithium-ion (Li-ion), nickel-hydrogen (N1-H2) batteries and the like.
  • an alkaline battery 10 comprises a generally cylindrical casing 20 having positive and negative terminals 22, 24 extending from opposite sides of casing 20.
  • Battery 10 may further include a protective cap 40, a pressure expansion seal 50 and a current collector 54, such as a brass pin.
  • the battery 10 includes an anode 60 and a cathode 70.
  • the cathode 70 may comprise, for example, a compressed paste of manganese dioxide with carbon powder added for increased conductivity.
  • Anode 60 may comprise, for example, a dispersion of zinc powder in a gel containing a potassium hydroxide electrolyte.
  • the hollow center of cathode 70 is lined with an ion conducting separator 75, which prevents contact of the electrode materials and short-circuiting of the cell.
  • Battery 10 may comprise one or more layers of separator 75, with each layer comprising fibers as described below.
  • FIGS. 2A-2C illustrate various embodiments of secondary batteries that may incorporate the separators described herein, such as rechargeable batteries including nickel- cadmium (Ni-Cd), nickel-metal hydride (Ni-MH), and lithium-ion (Li-ion).
  • rechargeable batteries including nickel- cadmium (Ni-Cd), nickel-metal hydride (Ni-MH), and lithium-ion (Li-ion).
  • Ni-Cd nickel- cadmium
  • Ni-MH nickel-metal hydride
  • Li-ion lithium-ion
  • FIG. 2A illustrates a cylindrical secondary battery 100 that includes a cathode 110, an anode 120 and a separator 130.
  • FIG. 2B illustrates a flat jelly roll secondary battery 200 that comprises a cathode 210, an anode 220 and a separator 230.
  • FIG. 2C illustrates a representative stacking arrangement 250 of unit cells 260 that each include a cathode 262, a separator 264 and an anode 266.
  • FIGS. 3A-3D illustrate alternative stacking arrangements for secondary or rechargeable batteries incorporated the separators described herein.
  • FIG. 3A illustrates a single sheet stacking arrangement 300 that comprises an anode 302, a cathode 304 and a separator 306.
  • FIG. 3B illustrates a Z-stacking arrangement 310 that comprises an anode 312, a cathode 314 and a separator 316.
  • the stacking process alternately stacks the cathode and anode and the separator through the sheet feeding mechanism to form stacked cores, which can produce regular-shaped or, for example, special-shaped lithium batteries with higher flexibility.
  • FIG. 3C illustrates a cylindrical winding stacking arrangement 320 that comprises an anode 322, a cathode 324 and a separator 326.
  • FIG. 3D illustrates a prismatic winding stacking arrangement 330 that comprises an anode 332, a cathode 334 and a separator 336.
  • the winding process generally comprises rolling the slitted cathode and anode and the separator together by controlling the speed, tension, relative position, etc. of the pole pieces. The characteristics of the process are particularly useful for lithium batteries with regular shapes.
  • a separator 80 for a battery comprises a first base layer 85 and a second coating layer 95.
  • Base layer 85 comprises polyvinyl alcohol (PVA) and cellulose.
  • PVA polyvinyl alcohol
  • the cellulose used in the base layer of the battery separator may include, but is not limited to, natural cellulose (wood fiber and pulp, cotton, hemp, etc.) and regenerated cellulose (e.g., rayon, viscose and/or Lyocell fibers).
  • the second layer could include nanofilaments, micro fibrillated cellulosic fibers, microcrystalline cellulose or microcrystalline cellulose gel combinations thereof.
  • the fibers of the second layer may be replaced or mixed with highly refined dissolving pulp or mercerized pulp, or a blend of these pulps with the cellulosic fibers.
  • the base layer may include PVA in a percentage (by dry weight) of about 20% to about 50%, or about 35% to about 45%. In an exemplary embodiment, the PVA is present in about 40% by dry weight.
  • the base layer may include cellulose in a percentage (by dry weight) of about 50% to about 80%, or about 55% to about 65%. In an exemplary embodiment, the cellulose comprises lyocell fibers present in about 60% by dry weight.
  • the PVA in the first layer initially comprises both water soluble PVA fibers and PVA fibers that are substantially insoluble at temperatures below about 40°C. This results in a first layer that comprises both PVA fibers and a water soluble PVA binder.
  • the PVA binder is generated by the water soluble PVA fibers that change shape as water evaporates from the separator.
  • the water insoluble PVA fibers maintain their shape during this evaporation process.
  • the first layer comprises about 20% to about 30% by dry weight nonsoluble PVA fibers, or about 25% by weight non-soluble PVA fibers, and about 10% to about 20% by weight soluble PVA binder, or about 15% by weight soluble PVA binder.
  • the non-soluble PVA fibers have a linear density greater than about 0.3 denier, or about 0.4 to about 0.6 denier, or about 0.5 denier. In other embodiments, the linear density is about 1 denier.
  • the base layer has a maximum pore size of less than about 5 ⁇ m prior to applying the coating layer (discussed below). In certain embodiments, the maximum pore size is less than about 3 ⁇ m, or about 2.8 ⁇ m or less.
  • the base layer has a mean pore size of less than about 1 ⁇ m, or about 0.6 ⁇ m or less prior to applying the coating layer.
  • the difference between the maximum pore size and a mean pore size of the base layer is less than about 3 ⁇ m, or equal to or less than about 2.2 ⁇ m.
  • separator 80 comprises the base layer 85 as described above and a second coating layer 95 comprising PVA and a polysaccharide .
  • the second layer is in contact with at least one major surface of the base layer, preferably a single side of the base layer.
  • the coating layer has a relatively low basis weight and thickness to mitigate the increase in ionic resistance across the separator.
  • the ratio of basis weight of the first layer to the second layer may be about 2 to about 12, or about 2 to about 5, or about 5 to about 8.
  • the polysaccharide used in the coating layer of the battery separator may include, but is not limited to, natural cellulose (wood fiber and pulp, cotton, hemp, etc.) and regenerated cellulose (e.g., rayon and Lyocell fibers).
  • the polysaccharide of the second layer may be nanofilaments, micro fibrillated cellulosic fibers or microcrystalline cellulose or cellulose gel.
  • the polysaccharide may comprise starch, carboxymethyl cellulose (CMC), hydroxypropyl methylcellulose (HPMC), alginate or combinations thereof.
  • the cellulose comprises microcrystalline cellulose gel having a basis weight of about 0.5 g/m 2 to about 8 g/m 2 , or about 1 g/m 2 to about 4 g/m 2 or about 3 g/m 2 .
  • the coating layer may include PVA in a percentage (by dry weight) of about 40% to about 60%, or about 45% to about 55%.
  • the PVA comprises high molecular weight PVA resin in about 50% by dry weight.
  • the coating layer may include cellulose in a percentage (by dry weight) of about 40% to about 60%, or about 45% to about 55%.
  • the cellulose comprises microcrystalline cellulose gel present in about 50% by dry weight.
  • the first layer essentially functions as a ground layer that provides liquid absorption properties and a relatively tight pore structure, while the coating functions as a finishing layer that further tightens the porous structure and provides improved short circuit shielding.
  • the separator (with the coating layer applied to a surface of the base layer) has a maximum pore size of less than about 2.0 ⁇ m, or less than about 1.8 ⁇ m or equal to or less than about 1.6 ⁇ m.
  • the mean pore size of the separator is less than about 1.0 ⁇ m or less than about 0.7 ⁇ m.
  • the difference between the maximum pore size and the mean pore size of the separator is less than about 2.0 ⁇ m, preferably less than about 1.0 ⁇ m.
  • the ionic resistance of the separator is less than about 100 mOhm-cm 2 , or less than about 95 mOhm-cm 2 , or less than about 90 mOhm-cm 2 , or less than about 80 mOhm-cm 2 , or less than about 60 mOhm-cm 2 .
  • the KOH absorption of the separator may be at least about 80 g/m 2 , or from about 80 g/m 2 to about 140 g/m 2 or about 100 g/m 2 to about 200 g/m 2 .
  • the Gurley Air Resistance of the separator is at least about 500 sec/100 ml, or at least about 750 sec/100 ml, or at least about 1,000 sec/100 ml, or at least about 1,450 sec/100 ml. This relatively high air resistance reduces the amount of air that passes through the separator, which improves the overall performance of the battery.
  • a method of making the separators described above includes a first step of forming a base layer by highly fibrillating a cellulose, for example, lyocell fibers, and optionally, cellulose.
  • the lyocell manufacturing process mainly consists of five steps (Fink el al. 2001; Rosenau el al. 2001; Biganska and Navard 2005; Bredereck and Hermanutz 2005; Hauru el al. 2014):
  • Dissolution This step includes the disintegration of the pulp fibers and mixing with the solvent.
  • Cellulose is dissolved in an aqueous system containing NMMO to form a dope of high viscosity.
  • the pulp dissolution for the lyocell process is much simpler than that of the viscose process, where the dissolution of dissolving pulp consists of the mercerization stage (steeping with sodium hydroxide), aging, and xanthation using carbon disulfide.
  • Cellulose fibrillation can be achieved using mechanical refiners such as a single disc refiner, a double disc refiner, a conical refiner, a rotating cylinder refiner, or other types of refiners used to mechanically grind or process cellulose or regenerated celluloses to fibrillate the fibers.
  • the feed material for this process may be previously treated cellulosic material (such as wood chips, annual plants, etc.) formed into pulp.
  • the previous treatment of the cellulosic material to produce pulp used as the feed material can be a result of chemical digestion, such as Kraft cooking, sulfite cooking, soda cooking, etc., mechanical refining, a combination of chemical digestion and refining, or other known processes.
  • a first layer is a wet laid paper layer.
  • the first layer can be formed from an aqueous suspension of PVA fibers, PVA binder and refined cellulose fibers.
  • the aqueous suspension of fibers in forming the first layer, is deposited onto a porous forming surface (such as a flat wire, incline wire or cylinder formers) that allows water to drain thereby forming the web.
  • a porous forming surface such as a flat wire, incline wire or cylinder formers
  • water is evaporated from the base layer and at least some portion of the PVA fibers (i.e., the water-soluble fibers) changes shape as the water evaporates to form a PVA binder.
  • a surfactant or wetting agent may subsequently be added after the drying of first layer by size-press, applicator roll, film-press, or spray to improve the wettability of the first layer, although in some embodiments, no wetting agent is used during this process.
  • Suitable surfactants include, but are not limited to, ethoxylated fatty alcohols, alkyl polyglycoside, such as cocamidopropyl betaine and the like.
  • the base layer material may be present in an amount between about 10 g/m 2 to 40g/m 2 , in embodiments, in amounts between about 20 to 25 g/m 2 .
  • a coating layer is created by blending water soluble polymers (e.g. polyvinyl alcohol resin) and microcrystalline cellulose gel, to create a blend of polyvinyl alcohol and microcrystalline cellulose gel.
  • a surfactant or wetting agent may subsequently be added to the blend to improve the wettability of the second layer, or, in some embodiments, no wetting agent is used during this process.
  • the second layer material may be present in an amount between 0.1 g/m 2 to 10 g/m 2 , in embodiments, in amounts between 2.5 to 5.0 g/m 2 , in yet another embodiment, in an amount that is about 3.0 to 3.5 g/m 2 .
  • the second layer is used to coat a single side of the first layer, preferably the top of the second layer, to further tighten the pore size while keeping the wet ionic resistance from increasing to undesirable ranges.
  • the coating technology used to apply the coating may be a bar coating, air knife coating, a curtain coating, a roll coater, slot die coater, spray coater, or a flexography printer with engraved anyloxed rolls.
  • lyocell fibers comprise about 60% by dry weight of the battery separator and the PVA fibers comprise about 40% by dry weight
  • the PVA fibers comprise about 25% by dry weight of the separator and the PVA binder comprises about 15% of the separator; and (2) a battery separator having a base layer of highly fibrillated lyocell fibers (i.e., cellulose) and polyvinyl alcohol (PVA) fibers and a PVA binder, wherein the lyocell fibers comprise about 60% by dry weight of the battery separator and the PVA fibers comprise about 40% by dry weight (“Single Layer”).
  • lyocell fibers i.e., cellulose
  • PVA polyvinyl alcohol
  • the PVA fibers comprise about 25% by dry weight of the separator and the PVA binder comprises about 15% of the separator; and a second coating layer of high molecular weight PVA resin and a polysaccharide wherein the PVA resin and the polysaccharide each comprise about 50% by dry weight of the second layer (“Bi-Layer”).
  • the polysaccharide is a microcrystalline cellulose gel.
  • the polysaccharide is a starch.
  • the polysaccharide is an alginate.
  • Applicant measured various parameters of the Single Layer and Bi-Layer battery separators, including the basis weight in g/m 2 in compliance with ISO standard 536:2012, the thickness under 100 kPa ( ⁇ m) in compliance with ISO standard 534:2011, the bulk index under 100 kPa [-] is calculated as a ratio of thickness to basis weight, the KOH Absorption in g/m 2 under a standard method of the industry which are further detailed below, the Gurley Air Resistance ⁇ s/100mL ⁇ in compliance with ISO standard 5636-5:2013, the mean pore size in ⁇ m, the largest or maximum pore size in ⁇ m, are measured according the description below.
  • the ratio and deltas of the maximum pore size to the mean pore size are calculated with the measured pore sizes.
  • the electrical resistance (mOhm-cm 2 ) is measured under standard methods of the industry which are further described below . All measurements were completed in an air-controlled room according to ISO 187: 1993. The results of these measurements are shown below in Table 1 (Single Layer) and Table 2 (Bi-Layer).
  • Separator material was cut into 100 mm x 100 mm square sheets. Specimen surface size was named A and its unit is m 2 Each 100 mm x 100 mm square specimen was individually weighed on a scale to determine the initial specimen weight. The initial specimen weight was named Wi. Then, each 100 mm x 100 mm specimen was individually soaked into a bath of caustic electrolyte. Such caustic electrolyte has a mass concentration of 34% Potassium Hydroxide and 2% Zinc Oxide. Electrolyte bath height was at least 1 cm. The whole 100 mm x 100 mm specimen was immerged flat and laid down flat at the bottom of the bath container for 10 minutes.
  • the mean pore size in ⁇ m and the max pore size in ⁇ m was measured using a capillary flow porometers.
  • the mean pore size is also named Mean Flow Pore Size and the max pore size is also named Bubble Point Diameter or Largest Pore Size.
  • a capillary flow porometer from Porous Materials INC., model IPore-1100 A with one holder setup was used to determine the mean pore size in ⁇ m and the max pore size in ⁇ m.
  • the determination of the mean pore size and the max pore size was performed according to the manual of IPore-1100A porometer with use of the dry and wet curves method.
  • the wetting liquid selected to determine the mean pore size and the max pore size was Galwick fluid having a surface tension of 15.9 dynes/cm.
  • the used pressure range was between 0 and 100 psi and maximum flow rate was 160000 cc/min.
  • PMI Capwin software it exists a default testing program. To characterize this invention this program with following modifications was used:
  • the electrical resistance in mOhm-cm 2 was determined according to ASTM D 7148A. In the literature, the electrical resistance in mOhm-cm 2 is also named ionic resistivity.
  • the electrical resistivity was determined by using a jig with two bottom and top right cylindrical graphite electrodes having a diameter of 1 inch and 1.25 inches respectively. Each electrode included a current collector inserted in one of its circular base areas; the current collectors were connected to an impedance tester using electrical cables.
  • the bottom electrode was immobile and mounted in a platform in such a way that one of its circular base areas was facing upwards, parallel to the ground and its opposite circular base area, having a current collector build in was facing downwards.
  • the second top electrode was mobile.
  • Each electrode’s circular base areas nonconnected to current collector was evenly polished using sandpaper.
  • the two graphite electrodes were placed vertically in such a way that their respective polished base areas were facing one another.
  • a caustic electrolyte was also used to determine the electrical resistance of a separator material.
  • the caustic electrolyte had a mass concentration of 40% Potassium Hydroxide.
  • the caustic electrolyte was applied on the bottom electrode polished base area in sufficient amount to cover the whole polished surface.
  • the second top electrode was set on top of the bottom electrode previously wetted using the caustic electrolyte in such a way that the caustic electrolyte formed a thin liquid interface in between the two electrodes.
  • the RC value was read on the impedance tester.
  • the total resistance of separator specimen, caustic electrolyte film and electrodes was noted RT in Ohm. RT was determined by placing a separator specimen previously soaked with the caustic electrolyte in between the two wetted electrodes. The RT value was read on the impedance tester.
  • the separator specimen had a disk shape and 1 inch diameter.
  • the separator specimen area was noted S and measured in cm 2 .
  • separator ER (RT — RC) - . Only one separator specimen was tested to
  • the single layer battery separator demonstrated reduced pore sizes, while maintaining the desirable wet ionic resistance and absorption performance.
  • the mean pore sizes of the separators were all equal to or less than about 0.6 ⁇ m and the maximum pore sizes were all equal to or less than about 2.8 ⁇ m.
  • the difference between the maximum and mean pore sizes ranged from about 1.7 ⁇ m to about 2.2 ⁇ m.
  • a wetting agent or surfactant was not present in the separator and the maximum pore size was only about 2.2 ⁇ m.
  • the electrical resistance of the separators were all less than 40 mOhm-cm 2
  • Gurley Air Resistance was in the range of 13 to 15 s/lOOmL and the KOH Absorption was between about 103 g/m 2 and 127 g/m 2 or
  • the Bi-Layer battery separator further reduced the mean and maximum pore sizes and the difference between the maximum and mean pore sizes (i.e., the pore size distribution) as compared to the Single Layer battery separator.
  • the maximum pore sizes of the Bi-Layer separators ranged from about 1.6 ⁇ m to about 0.1 ⁇ m.
  • the difference between maximum and mean pore sizes were less in the Bi-Layer samples than the difference between maximum and mean pore sizes in the Single Layer samples.
  • the BiLayer samples had a tighter pore size distribution.
  • the delta between maximum pore sizes and mean pore sizes in samples 2 and 3 samples was about 0.6 ⁇ m and 0.9 ⁇ m, respectively.
  • sample 1 a wetting agent or surfactant was not present in the separator and the maximum pore size was only about 0.1 ⁇ m.
  • the electrical resistance for the Bi-Layer samples ranged from about 41-90 mOhm-cm 2 .
  • the KOH absorption ranged from about 86 to about 119 g/m 2
  • the Gurley Air Resistance ranged from about 500 to over 45,000 second /100 mL.
  • the Bi-Layer samples had a significantly increased air resistance as compared to the single layer samples, which results in a substantial improvement to the performance of the battery.
  • a first embodiment is a two-layer battery separator comprising a first layer comprising about 20% to about 50% by weight polyvinyl alcohol and about 50% to about 80% by weight cellulose based on the total dry weight of the first layer and a second layer in contact with a surface of the first layer and comprising polyvinyl alcohol and a polysaccharide.
  • the separator has a maximum pore size of less than about 2.0 ⁇ m.
  • a second embodiment is the first embodiment, wherein the maximum pore size is less than or equal to about 1.6 ⁇ m.
  • a third embodiment is any combination of the first 2 embodiments, wherein a mean pore size of the separator is less than about 1.0 ⁇ m
  • a 4 th embodiment is any combination of the first 3 embodiments, wherein the mean pore size is equal to or less than about 0.7 ⁇ m.
  • a 5 th embodiment is any combination of the first 4 embodiments, wherein a difference between the maximum pore size and a mean pore size of the separator is less than about 2.0 ⁇ m.
  • a 6 th embodiment is any combination of the first 5 embodiments, wherein a difference between the maximum pore size and a mean pore size of the separator is less than about 1.0 ⁇ m.
  • a 7 th embodiment is any combination of the first 6 embodiments, wherein the second layer comprises a coating adhered to the surface of the first layer.
  • An 8 th embodiment is any combination of the first 7 embodiments, wherein the first layer comprises about 35% to about 45% by weight polyvinyl alcohol and about 55% to about 65% by weight cellulose or a regenerated cellulose.
  • a 9 th embodiment is any combination of the first 8 embodiments, wherein the first layer comprises about 40% by weight polyvinyl alcohol and about 60% by weight cellulose or a regenerated cellulose.
  • a 10 th embodiment is any combination of the first 9 embodiments, wherein the PVA in the first layer comprises soluble and non-soluble PVA fibers.
  • An 11 th embodiment is any combination of the first 10 embodiments, wherein the first layer comprises about 20% to about 30% by weight non-soluble PVA fibers and about 10% to about 20% by weight soluble PVA fibers.
  • a 12 th embodiment is any combination of the first 11 embodiments, wherein the non-soluble PVA fibers are about 25% by weight of the first layer and the soluble PVA fibers are about 15% by weight of the first layer.
  • a 13 th embodiment is any combination of the first 12 embodiments, wherein the non-soluble PVA fibers have a linear density greater than about 0.3 denier.
  • a 14 th embodiment is any combination of the first 13 embodiments, wherein the linear density is about 0.4 denier to about 0.6 denier.
  • a 15 th embodiment is any combination of the first 14 embodiments, wherein the linear density is about 0.5 denier.
  • a 16 th embodiment is any combination of the first 15 embodiments, wherein the polysaccharide comprises a material selected from a group consisting of cellulose fibers, cellulose nanofilaments, microcrystalline cellulose, microcrystalline cellulose gel, starch, carboxymethyl cellulose (CMC), hydroxypropyl methylcellulose (HPMC), alginate, micro fibrillated cellulosic fibers or combinations thereof.
  • the polysaccharide comprises a material selected from a group consisting of cellulose fibers, cellulose nanofilaments, microcrystalline cellulose, microcrystalline cellulose gel, starch, carboxymethyl cellulose (CMC), hydroxypropyl methylcellulose (HPMC), alginate, micro fibrillated cellulosic fibers or combinations thereof.
  • a 17 th embodiment is any combination of the first 16 embodiments, wherein the second layer comprises about 45% to about 55% by dry weight polyvinyl alcohol and about 45% to about 55% by dry weight cellulose.
  • a 18 th embodiment is any combination of the first 17 embodiments, wherein the second layer comprises about 50% by dry weight polyvinyl alcohol and about 50% by dry weight cellulose.
  • a 19 th embodiment is any combination of the first 18 embodiments, wherein the PVA in the second layer comprises a water soluble PVA resin and the polysaccharide comprises a microcrystalline cellulose gel.
  • a 20 th embodiment is any combination of the first 19 embodiments, wherein a ratio of a basis weight of the first layer to a basis weight of the second layer is about 2 to about 12.
  • a 21 st embodiment is any combination of the first 20 embodiments, wherein the ratio is about 5 to about 8.
  • An 22 nd embodiment is any combination of the first 21 embodiments, wherein the first layer does not contain a surfactant and the maximum pore size is less than about 0.2 ⁇ m.
  • a 23 rd embodiment is any combination of the first 22 embodiments, wherein a maximum pore size of the separator is about 0.1 ⁇ m or less.
  • a 24 th embodiment is any combination of the first 23 embodiments, wherein the ionic resistance of the separator is less than about 100 mOhm-cm 2 .
  • a 25 th embodiment is any combination of the first 24 embodiments, wherein a KOH absorption of the separator is at least about 80 g/m 2
  • a 26 th embodiment is any combination of the first 25 embodiments, wherein a Gurley Air Resistance of the separator is at least about 500 second / 100 mL, or at least about 1000 second / 100 mL.
  • a 27 th embodiment is any combination of the first 26 embodiments, wherein the Gurley Air Resistance is at least about 1400 second / 100 mL.
  • a primary battery comprising the battery separator of any of the above 27 embodiments.
  • a secondary battery comprising the battery separator of any of the above 27 embodiments.
  • a stationary battery comprising the battery separator of any of the above 27 embodiments.
  • an alkaline battery comprising the battery separator of any of the above 27 embodiments.
  • a first embodiment is a two-layer battery separator comprising a first layer comprising about 20% to about 50% by weight polyvinyl alcohol and about 50% to about 80% by weight cellulose or a regenerated cellulose and a second layer in contact with a surface of the first layer and comprising polyvinyl alcohol fibers and a polysaccharide.
  • the difference between a maximum pore size and a mean pore size of the separator is less than about 2.0 ⁇ m.
  • a second embodiment is the first embodiment, wherein the difference between the maximum pore size and the mean pore size of the separator is less than about 1.0 ⁇ m.
  • a 3 rd embodiment is any combination of the first 2 embodiments, wherein a ratio of the maximum pore size to the mean pore size is about 1.0 to about 4.0.
  • a 4 th embodiment is any combination of the first 3 embodiments, wherein the ratio is about 1.5 to about 2.5.
  • a 5 th embodiment is any combination of the first 4 embodiments, wherein the first layer comprises about 35% to about 45% by weight polyvinyl alcohol and about 55% to about 65% by weight cellulose fibers or a regenerated cellulose.
  • a 6 th embodiment is any combination of the first 5 embodiments, wherein the first layer comprises about 40% by weight polyvinyl alcohol and about 60% by weight cellulose fibers or a regenerated cellulose.
  • a 7 th embodiment is any combination of the first 6 embodiments, wherein the polysaccharide comprises a material selected from a group consisting of cellulose fibers, cellulose nanofilaments, microcrystalline cellulose, microcrystalline cellulose gel, starch, carboxymethyl cellulose (CMC), hydroxypropyl methylcellulose (HPMC), alginate, micro fibrillated cellulosic fibers or combinations thereof.
  • the polysaccharide comprises a material selected from a group consisting of cellulose fibers, cellulose nanofilaments, microcrystalline cellulose, microcrystalline cellulose gel, starch, carboxymethyl cellulose (CMC), hydroxypropyl methylcellulose (HPMC), alginate, micro fibrillated cellulosic fibers or combinations thereof.
  • An 8 th embodiment is any combination of the first 7 embodiments, wherein the second layer comprises about 45% to about 55% by weight polyvinyl alcohol and about 45% to about 55% by weight cellulose.
  • a 9 th embodiment is any combination of the first 8 embodiments, wherein the second layer comprises about 50% by weight polyvinyl alcohol resin and about 50% by weight microcrystalline cellulose gel.
  • a 10 th embodiment is any combination of the first 9 embodiments, wherein the second layer comprises a coating adhered to the surface of the first layer.
  • a primary battery comprising the battery separator of any of the above 10 embodiments.
  • a secondary battery comprising the battery separator of any of the above 10 embodiments.
  • a stationary battery comprising the battery separator of any of the above 10 embodiments.
  • an alkaline battery comprising the battery separator of any of the above 10 embodiments.
  • a first embodiment is a battery separator comprising a first layer comprising about 20% to about 50% by weight polyvinyl alcohol and about 50% to about 80% by weight cellulose or a regenerated cellulose and a coating in contact with a surface of the first layer and comprising polyvinyl alcohol and a polysaccharide, wherein a ratio of a basis weight of the first layer to a basis weight of the coating is about 2 to about 12.
  • a second embodiment is the first embodiment, wherein the ratio of basis weight is about 5 to about 8.
  • a third embodiment is any combination of the first 2 embodiments, wherein the separator consists of the first layer and the coating.
  • a 4 th embodiment is any combination of the first 3 embodiments, wherein the separator has a maximum pore size of less than about 2.0 ⁇ m.
  • a 5 th embodiment is any combination of the first 4 embodiments, wherein the maximum pore size is less than about 1.6 ⁇ m.
  • a 6 th embodiment is any combination of the first 5 embodiments, wherein a mean pore size of the separator is less than about 1.0 ⁇ m.
  • a 7 th embodiment is any combination of the first 6 embodiments, wherein a difference between the maximum pore size and the mean pore size of the separator is less than about 1.0 ⁇ m.
  • An 8 th embodiment is any combination of the first 7 embodiments, wherein the first layer comprises about 40% by weight polyvinyl alcohol and about 60% by weight cellulose fibers.
  • a 9 th embodiment is any combination of the first 8 embodiments, wherein the coating comprises about 50% by weight polyvinyl alcohol and about 50% by weight microcrystalline cellulose gel.
  • an alkaline or stationary battery comprising the battery separator of the first 9 embodiments.
  • a first embodiment is a battery separator comprising a first layer comprising about 20% to about 50% by weight polyvinyl alcohol (PVA) fibers and about 50% to about 80% by weight cellulose or a regenerated cellulose, wherein the PVA fibers have a linear density greater than about 0.3 denier and a second layer in contact with a surface of the first layer and comprising polyvinyl alcohol and a polysaccharide.
  • PVA polyvinyl alcohol
  • a second embodiment is the first embodiment, wherein the first layer comprises a PVA binder and the PVA fibers.
  • a 3 rd embodiment is any combination of the first 2 embodiments, wherein the linear density of the PVA fibers in the first layer is about 0.4 denier to about 0.6 denier.
  • a 4 th embodiment is any combination of the first 3 embodiments, wherein the linear density of the PVA fibers in the first layer is about 0.5 denier.

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Cell Separators (AREA)

Abstract

L'invention concerne des batteries, des séparateurs de batteries et des procédés de fabrication de tels séparateurs. Les séparateurs peuvent être utilisés dans diverses batteries primaires et secondaires. Un séparateur de batterie comprend une couche de base comprenant environ 20 % à environ 50 % en poids d'alcool polyvinylique (PVA) et environ 50 % à environ 80 % en poids de cellulose ou d'une cellulose et une seconde couche en contact avec la première couche et comprenant du PVA et un polysaccharide. Le séparateur a une taille de pore maximale inférieure à environ 2 µm et une taille de pore moyenne inférieure à environ 1 µm. La différence entre les tailles de pores maximale et moyenne est inférieure à environ 2 µm, ce qui diminue la distribution globale des tailles de pores dans le séparateur, améliorant ainsi les performances de celui-ci.
PCT/US2024/055626 2023-11-14 2024-11-13 Séparateurs de batterie à tailles de pores réduites Pending WO2025106476A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130183569A1 (en) * 2010-09-16 2013-07-18 Kuraray Co., Ltd Alkaline battery separator and alkaline battery using separator
US20180331340A1 (en) * 2017-05-11 2018-11-15 Lydall, Inc. Multilayer battery separator and method of making same
US20230086918A1 (en) * 2021-09-17 2023-03-23 Mativ Holdings, Inc. Multi-layer battery separator

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130183569A1 (en) * 2010-09-16 2013-07-18 Kuraray Co., Ltd Alkaline battery separator and alkaline battery using separator
US20180331340A1 (en) * 2017-05-11 2018-11-15 Lydall, Inc. Multilayer battery separator and method of making same
US20230086918A1 (en) * 2021-09-17 2023-03-23 Mativ Holdings, Inc. Multi-layer battery separator

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