CA2952434C - Anti-sulphation pasting mats for lead-acid batteries - Google Patents
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- CA2952434C CA2952434C CA2952434A CA2952434A CA2952434C CA 2952434 C CA2952434 C CA 2952434C CA 2952434 A CA2952434 A CA 2952434A CA 2952434 A CA2952434 A CA 2952434A CA 2952434 C CA2952434 C CA 2952434C
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- 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
- H01M50/44—Fibrous material
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- 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
- H01M10/06—Lead-acid accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/68—Selection of materials for use in lead-acid accumulators
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4209—Inorganic fibres
- D04H1/4218—Glass fibres
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/587—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/732—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by fluid current, e.g. air-lay
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
- D06M13/256—Sulfonated compounds esters thereof, e.g. sultones
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
- D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0011—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using non-woven fabrics
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- 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
- H01M10/06—Lead-acid accumulators
- H01M10/12—Construction or manufacture
- H01M10/14—Assembling a group of electrodes or separators
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- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
- H01M4/806—Nonwoven fibrous fabric containing only fibres
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- 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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- 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
- H01M50/431—Inorganic material
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- 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
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2201/00—Chemical constitution of the fibres, threads or yarns
- D06N2201/08—Inorganic fibres
- D06N2201/082—Glass fibres
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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- D06N2203/00—Macromolecular materials of the coating layers
- D06N2203/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06N2203/045—Vinyl (co)polymers
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- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
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- D10B2505/00—Industrial
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
- H01M4/16—Processes of manufacture
- H01M4/20—Processes of manufacture of pasted electrodes
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- 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
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Abstract
A non-woven fiber mat for lead-acid batteries is provided. The non-woven fiber mat includes glass fibers coated with a sizing composition, a binder composition, and organic active compounds, wherein the organic active compounds are effective in reducing or preventing sulphation in lead-acid batteries.
Description
ANTI-SULPHATION PASTING MATS FOR LEAD-ACID BATTERIES
FIELD
[0001] The general inventive concepts relate to lead-acid batteries, and more particularly to non-woven fiber mats for use in lead-acid batteries. The non-woven fiber mats reduce the occurrence of sulphation in lead-acid batteries.
BACKGROUND
FIELD
[0001] The general inventive concepts relate to lead-acid batteries, and more particularly to non-woven fiber mats for use in lead-acid batteries. The non-woven fiber mats reduce the occurrence of sulphation in lead-acid batteries.
BACKGROUND
[0002] Lead-acid batteries are among the most commonly used rechargeable batteries due to their ability to supply high currents, while having a relatively low production cost. Lead-acid batteries are largely used in the automotive starting, lighting, and ignition (SLI) sector and in other industrial sectors due to their high discharge capability. Conventional lead-acid batteries include a positive electrode (Pb02 plate) and a negative electrode (spongy Pb plate) immersed in a sulfuric acid electrolyte. A separator may be disposed between the positive and negative plates. Separators function to not only provide mechanical separation between the positive and negative plates, but to also prevent shorting between electrodes and allow ionic conduction. There are many different forms of electrodes. In some instances, the electrodes consist of lead or lead alloy plates having a grid-like structure. An active material paste consisting of lead oxides and sulfuric acid may be used to fill the holes in the grid of the positive plate. The active material paste is porous, thereby allowing the acid to react with the lead inside the plate, which increases the surface area of the electrodes. The paste is dried and the positive and negative electrodes are activated by an electrochemical process.
[0003] During discharge, both the positive and negative plates react with the acid electrolyte material causing lead (II) sulfate (PbSO4) to coat the plates. Lead sulfate is a soft material that can be re-converted back into lead and sulfuric acid, provided the discharged battery is reconnected to a battery charger in a timely manner. As current is applied to re-charge a lead-acid battery, the lead sulfate partially reverses back to lead and lead oxide.
This partial reversal to their original states "recharges" the positive and negative electrodes.
This partial reversal to their original states "recharges" the positive and negative electrodes.
[0004] If a lead-acid battery is left in the discharged state for a prolonged period of time, the lead sulfate will begin to form hard crystals and coat the surface of the electrode plates. Such a period of prolonged lead sulfate exposure may occur, for instance, when a lead-acid battery is deprived of a full charge. Because hard lead sulfate is a non-conductive material, when it coats the electrode plates, it causes a reduction in the area needed for the electro-chemical reactions. Additionally, the large crystals can reduce the battery's active material that is responsible for high capacity and low resistance.
[0005] There have been numerous attempts to reduce detrimental sulphation in lead-acid batteries. For example, paper has been applied to the plate to control the active material on the grid. For example, traditionally, a cellulosic paper may be applied to the plates to aid in spreading the active material paste, keep moisture in the plate prior to drying and to keep the paste on the grid prior to assembling the battery. However, due to the interference of the pasting paper with the battery performance, the paper is either discarded prior to assembly of the battery or degrades during use. This often causes a disruption in the operation of the battery by interfering with the chemical reactions and/or clogging the electrodes.
SUMMARY
SUMMARY
[0006] Various aspects of the general inventive concepts are directed to a non-woven fiber pasting mat for lead-acid batteries. The non-woven fiber pasting mats include a plurality of glass fibers coated with a sizing composition, a binder composition, and one or more organic active compounds. In some exemplary embodiments, the organic active compounds reduce sulphation in lead-acid batteries.
10007] In some exemplary embodiments, the organic active compounds are included in at least one of the sizing composition and the binder composition, [0008] In some exemplary embodiments, the organic active compounds comprise one or more of sulphosuccinate (di-octyl); polyvinylalcohol; colloidal silica;
polyacrylamide;
phosphonic acid; polyacrylic acid, such as polycarboxylate and anionic polyelectolyte;
phosphate ester; polycarboxylic acid, such as acrylic, maleic, lactic, tartaric, etc.; polymeric anionic compounds, such as polyvinylsulphonic acid and poly(meth)acrylic acid;
hexamethylenediaminetetralds; chitin; chitosan; inulin; polyaspartic acid;
polysuccinimide;
iminodisuccinate; maleic acid/acrylic acid copolymer; maleic acid/acrylamide copolymer;
humic acid; calcium salt of polymers from naphtalenenesulphonic acid condensed with formaldehyde; sodium salt of condensed sulfonated naphtalene;
perfluoroallcylsulfonic acid;
and cellulose.
[0009] Various aspects of the general inventive concepts are directed to a lead-acid battery that includes at least one positive electrode and at least one negative electrode immersed within an electrolyte and a non-woven glass fiber pasting mat at least partially covering a surface of at least one of the positive and negative electrode. The non-woven fiber pasting mat includes a plurality of glass fibers coated with a sizing composition, a binder composition, and one or more organic active compounds.
In some exemplary embodiments, the organic active compounds reduce formation of lead sulphate on said negative electrode.
[0010] In some exemplary embodiments, said organic active compounds are included in at least one of the sizing composition and the binder composition.
[0011] Various exemplary embodiments of the general inventive concepts are further directed to a method of forming an anti-sulphation pasting mat for use in a lead-acid battery. The method includes dispersing a plurality of glass fibers into an aqueous slurry, said glass fibers being coated with a sizing composition;
depositing the slurry onto a moving screen; applying a binder onto the deposited slurry; and heating the binder-coated slurry, thereby curing the binder and forming a non-woven pasting mat. The pasting mat includes one or more organic active compounds included in at least one of the sizing composition and the binder.
[0012] In some exemplary embodiments, the non-woven fiber pasting mat is capable of increasing the life cycle of a lead-acid battery by at least 10% compared to an otherwise comparable battery without the pasting mat.
10012a] In one aspect, there is provided a non-woven fiber pasting mat comprising: a plurality of fibers coated with a sizing composition, wherein the sizing composition is coated on the plurality of fibers by a process that includes applying an aqueous-based suspension or emulsion comprising a film former selected from a group consisting of polyvinyl acetates, polyurethanes, modified polyolefins, polyesters epoxides, and mixtures thereof, to the plurality of fibers; a binder composition applied onto the coated fibers, wherein the binder composition is different from the sizing composition; and one or more organic active compounds included in at least one of said sizing composition and said binder composition, said organic active compounds comprising one or more of di-octyl sulphosuccinate;
polyvinylalcohol; colloidal silica;
polyacrylamide; phosphonic acid; polyacrylic acid; phosphate ester;
polycarboxylic acid; polymeric anionic compounds; hexamethylenediaminetetrakis-(methylenephosphonic acid); chitin;
chitosan; mull;
polyaspartic acid; polysuccinimide; iminodisuccinate; maleic acid/acrylic acid copolymer; maleic acid/acrylamide copolymer; humic acid; calcium salt of polymers from naphtalenenesulphonic acid condensed with formaldehyde; sodium salt of condensed sulfonated naphtalene;
perfluoroalkylsulfonic acid; and cellulose, wherein the binder composition holds the fibers together to form said non-woven mat, and wherein said one or more organic active compounds operate to reduce sulphation in a lead-acid battery.
Date Recue/Date Received 2022-06-22 [0012b] In another aspect, there is provided a lead-acid battery comprising: a positive electrode having a first face and a second face opposite said first face and a negative electrode having a first face and a second face opposite said first face, wherein each of said positive and negative electrode is immersed within an electrolyte; a non-woven fiber pasting mat at least partially covering a surface of at least one of said first and second faces of at least one of said positive and said negative electrode, said non-woven fiber pasting mat comprising: a plurality of fibers coated with a sizing composition, wherein the sizing composition is coated on the plurality of fibers by a process that includes applying an aqueous-based suspension or emulsion comprising a film former selected from a group consisting of polyvinyl acetates, polyurethanes, modified polyolefins, polyesters epoxides, and mixtures thereof, to the plurality of fibers; a binder composition applied onto the coated fibers; wherein the binder composition is different from the sizing composition; and one or more organic active compounds included in at least one of said sizing composition and said binder composition, said organic active compounds comprising one or more of di-octyl sulphosuccinate; polyvinylalcohol; colloidal silica; polyacrylamide;
phosphonic acid; polyacrylic acid;
phosphate ester; polycarboxylic acid; polymeric anionic compounds;
hexamethylenediaminetetrakis-(methylenephosphonic acid); chitin; chitosan; inulin; polyaspartic acid;
polysuccinimide; iminodisuccinate;
maleic acid/acrylic acid copolymer; maleic acid/acrylamide copolymer; humic acid; calcium salt of polymers from naphtalenenesulphonic acid condensed with formaldehyde; sodium salt of condensed sulfonated naphtalene; perfluoroalkylsulfonic acid; and cellulose, wherein the binder composition holds the fibers together to form the non-woven fiber pasting mat, and wherein said one or more organic active compounds operate to reduce sulphation in the lead-acid battery.
[0012c1 In another aspect, there is provided a method of forming a non-woven fiber mat for use in a lead-acid battery, said method comprising: dispersing a plurality of fibers into an aqueous slurry, said fibers being coated with a sizing composition, wherein the sizing composition is an aqueous based suspension or emulsion comprising a film former selected from a group consisting of polyvinyl acetates, polyurethanes, modified polyolefins, polyesters epoxides, and mixtures thereof; depositing said slurry onto a screen;
applying a binder onto the fibers of the deposited slurry, wherein the binder is different from the sizing composition; and heating said deposited slurry, thereby curing said binder on the fibers of the deposited slurry and forming said non-woven fiber mat, wherein said fiber mat includes one or more organic active compounds included in at least one of said sizing composition and said binder, said organic active compounds comprising one or more of di-octyl sulphosuccinate;
polyvinylalcohol; colloidal silica;
polyacrylamide; phosphonic acid; polyacrylic acid; phosphate ester;
polycarboxylic acid; polymeric anionic compounds; hexamethylenediaminetetrakis-(methylenephosphonic acid); chitin;
chitosan; inulin;
polyaspartic acid; polysuccinimide; iminodisuccinate; maleic acid/acrylic acid copolymer; maleic acid/
Date Regue/Date Received 2022-10-26 acrylamide copolymer; humic acid; calcium salt of polymers from naphtalenenesulphonic acid condensed with formaldehyde; sodium salt of condensed sulfonated naphtalene;
perfluoroalkylsulfonic acid; and cellulose.
10012d] In another aspect, there is provided a non-woven retainer mat for contacting a separator in a lead-acid battery comprising: a plurality of fibers coated with a sizing composition, wherein the sizing composition is coated on the plurality of fibers by a process that includes applying an aqueous-based suspension or emulsion comprising a film former selected from a group consisting of polyvinyl acetates, polyurethanes, modified polyokfins, polyesters epoxides, and mixtures thereof, to the plurality of fibers; a binder composition applied onto the coated fibers, wherein the binder composition is different from the sizing composition; and one or more additives included in at least one of said sizing composition and said binder composition, said one or more additives comprising one or more of di-octyl sulphosuccinate;
polyvinylakohol; colloidal silica; polyacrylamide; phosphonic acid;
polyacrylic acid; phosphate ester;
polycarboxylic acid; polymeric anionic compounds; hexamethylenediaminetetrakis-(methylenephosphonic acid); chitin; chitosan; inulin; polyaspartic acid; polysuccinimide;
iminodisuccinate; maleic acid/acrylic acid copolymer; maleic acid/acrylamide copolymer; humic acid; calcium salt of polymers from naphtalenenesulphonic acid condensed with formaldehyde; sodium salt of condensed sulfonated naphtalene; perfluoroalkylsulfonic acid; rubber additives; rubber derivatives;
aldehydes; aldehyde derivatives; metals salts; fatty alcohol ethyloxylates; ethylene-propylene oxide block copolymers; sulphate esters; sulphonate esters; sulphosuccinates; lignin; lignin derivatives;
phenol formaldehyde resin; wood flour; and cellulose, wherein the binder composition holds the fibers together to form the non-woven retainer mat, and wherein said one or more additives operate to reduce sulphation in the lead-acid battery.
[0012e1 In another aspect, there is provided a lead-acid battery comprising: a positive electrode, a negative electrode, and a separator, having a first face and a second face opposite thereto, disposed therebetween, wherein each of the positive electrode negative electrode, and separator is immersed within an electrolyte;
and the non-woven retainer mat described herein.
100131 Additional features and advantages will be set forth in part in the description that follows, and in part may be obvious from the description, or may be learned by practice of the exemplary embodiments disclosed herein. It is to be understood that both the foregoing summary and the following detailed description are explanatory only and are not restrictive of the general inventive concepts as disclosed herein or as claimed.
4a Date Recue/Date Received 2022-06-22 DESCRIPTION OF THE DRAWINGS
[0014] Example embodiments of the invention will be apparent from the more particular description of certain example embodiments of the invention provided below and as illustrated in the accompanying drawings.
[0015] Figure 1 graphically illustrates the electrical resistance normalized over 0.10 mm thickness for exemplary non-woven fiber mats prepared in accordance with the present invention.
DETAILED DESCRIPTION
[0016] Various exemplary embodiments will now be described more fully, with occasional reference to any accompanying drawings. These exemplary embodiments may, however, be embodied in different forms and should not be construed as limited to the descriptions set forth herein.
Rather, these exemplary embodiments are provided so that this disclosure will be thorough and complete, and will convey the general inventive concepts to those skilled in the art.
[0017] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which these exemplary embodiments belong.
The terminology used in the description herein is for describing particular exemplary embodiments only and is not intended to be limiting of the exemplary embodiments.
[0018] As used in the specification and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
[0019] Unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about" Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present exemplary embodiments. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should be construed in light of the number of significant digits and ordinary rounding approaches.
[0020] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the exemplary embodiments are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. Every numerical range given throughout this specification and claims will include every narrower numerical range that falls within such 4b Date Recue/Date Received 2022-06-22 broader numerical range, as if such narrower numerical ranges were all expressly written herein.
[0021] The general inventive concepts relate to a non-woven fiber mat, such as a pasting mat or a retainer mat, or other batteries. The non-woven fiber mat may comprise a plurality of reinforcement fibers combined in the form of a sheet. In some exemplary embodiments, the reinforcement fibers are made from glass. However, the reinforcement fibers may also include synthetic fibers, or a combination of glass fibers and synthetic fibers. The term synthetic fiber, as used herein, is intended to include any man-made fiber having suitable reinforcing characteristics including fibers made from suitable polymers such as, for example, polyesters, polyolefins, nylons, aramids, poly(phenylene sulfide), and suitable non-glass fibers such as, carbon, silicon carbide (SiC) and boron nitride.
100221 The glass fibers may be formed from any type of glass suitable for a particular application and/or desired product specifications, including conventional glasses. Non-exclusive examples of glass fibers include A-type glass fibers, C-type glass fibers, G-type glass fiber, E-type glass fibers, S-type glass fibers, E-CR-type glass fibers (e.g., Advantexe glass fibers commercially available from Owens Corning), R-type glass fibers, wool glass fibers, biosoluble glass fibers, and combinations thereof, which may be used as the reinforcing fiber. In some exemplary embodiments, the glass fibers are durable in an acidic environment.
[0023] The non-woven glass fiber mat may comprise a single mat, or more than one mat, e.g., two, three, four, or five mats, which may be employed in a single lead-acid battery. Each non-woven glass fiber mat may comprise a single layer, or may be composed of more than one layer, e.g., two, three, four, or five layers. In some exemplary embodiments, the non-woven fiber mat comprises a non-woven glass fiber pasting mat. In some exemplary embodiments, the non-woven fiber mat comprises a non-woven glass fiber retainer mat.
[0024] In some exemplary embodiments, the glass fibers have a diameter that is at least 0.2 microns, such as from 0.2 to 30 microns. In some exemplary embodiments, the glass fibers have a diameter from about 1 to about 25 microns, or from about 6 to about 23 microns.
100251 Glass fibers may be formed by drawing molten glass into filaments through a bushing or orifice plate and applying a sizing composition to the filaments as they solidify. The sizing composition provides protection to the fibers from interfilament abrasion and promotes compatibility between the glass fibers and the matrix in which the glass fibers are to be used.
After the sizing composition is applied, the fibers may be gathered into one or more strands and wound into a package or, alternatively, the fibers may be chopped while wet with the sizing and collected. The collected chopped strands may then be dried to form dry chopped fibers or they can be packaged in their wet condition as wet chopped fibers.
100261 In some exemplary embodiments, the sizing compositions used to coat glass fibers are aqueous-based compositions, such as suspensions or emulsions. The suspension or emulsion has a solids content that may be composed of one or more of a film former, a coupling agent, a lubricant, and a surfactant. A film former may work to hold individual filaments together to form fibers, and protect the filaments from damage caused by abrasion.
Acceptable film formers include, for example, polyvinyl acetates, polyurethanes, modified polyolefins, polyesters epoxides, and mixtures thereof A coupling agent may be included in a sizing composition to enhance the adhesion of the sizing composition with a matrix material when forming a composite, to improve the composite properties. In some exemplary embodiments, the coupling agent is an organofunctional silane.
10027] Additional additives may be included in the sizing compositions, depending on the intended application. Such additives include, for example, anti-statics, wetting agents, antioxidants, and pH modifiers.
100281 In accordance with the general inventive concepts, the non-woven glass fiber mat may be produced using either continuous or chopped fibers, or a combination of the continuous and chopped fibers. The chopped fibers or fiber strands have lengths that may vary depending on a particular process and/or application. In some exemplary embodiments, the chopped fibers/strands have a length of about 3 to about 60 mm.
10029] The non-woven glass fiber mats may be formed in accordance with any of the known methods for producing glass fiber mats, such as wet-laid processing and dry-laid processing.
In a wet-laid processing, a water slurry (i.e., "whitewater") is provided into which glass fibers are dispersed. The white water may contain dispersants, viscosity modifiers, defoaming agents or other chemical agents. The slurry containing the glass fibers is then deposited onto a moving screen and a substantial amount of the water is removed. A binder may then be applied to the deposited fibers and the resulting mat is dried to remove any remaining water and to cure the binder, forming a non-woven glass fiber mat. In a dry-laid process, fibers are chopped and air blown onto a conveyor and a binder is then applied to form a mat. Dry-laid processes may be particularly suitable for the production of highly porous mats having bundles of glass fibers.
[0030] The binder may be any type of binder composition, such as an acrylic binder, a styrene acrylonitrile binder, a styrene butadiene rubber binder, a urea formaldehyde binder, an epoxy binder, a polyurethane binder, a phenolic binder, a polyester binder, or mixtures thereof. Exemplary acrylic binders may include, for example, polyacrylic acid, ethylacrylate, methacrylate, methylmethacrylate, styrene acrylate, or mixtures thereof. In some exemplary embodiments, the binder is a thermoset acrylic binder formed of polyacrylic acid and at least one polyol, such as for example, triethanolamine or glycerine. The binder may optionally contain one or more additives for improving processibility and/or product performance. Non-limiting examples of such additives include dyes, oils, fillers, colorants, UV
stabilizers, coupling agents (for example, aminosilanes), lubricants, wetting agents, surfactants, antistatic agents, and combinations thereof.
100311 In some exemplary embodiments, the binder comprises about 1 to about 30 weight percent of the total dry weight of the glass fiber mat. In other exemplary embodiments, the binder comprises about 8 to about 25 weight percent of the total dry weight of the glass fiber mat. In some exemplary embodiments, the binder comprises about 18 to 25 weight percent of the total dry weight of the glass fiber mat.
[0032] In some exemplary embodiments, the non-woven glass fiber mats are treated with one or more organic active compounds that are capable of reducing or eliminating sulphation of the electrodes in a lead-acid battery. The organic active compounds may be included as additives to the sizing composition, additives to the binder composition, or as an additive to both the sizing and binder compositions. In some exemplary embodiments, the additives may be added to the surface of the mat, after the mat has been formed.
[0033] In some exemplary embodiments, the organic active compounds include active ingredients that directly influence the reactions that take place on the surface of an electrode.
In some exemplary embodiments, the organic active compounds include one or more of sulphosuccinate (di-octyl); polyvinylalcohol; colloidal silica;
polyacrylamide; phosphonic acid; polyacrylic acid, such as polycarboxylate and anionic polyelectolyte;
phosphate ester;
polycarboxylic acid, such as acrylic, maleic, lactic, tartaric, etc.;
polymeric anionic compounds, such as polyvinylsulphonic acid and poly(meth)acrylic acid;
hexamethylenediaminetetrakis; chitin; chitosan;
polyaspartic acid; polysuccinimide;
iminodisuccinate; maleic acid/acrylic acid copolymer; maleic acid/acrylamide copolymer;
humic acid; calcium salt of polymers from naphtalenenesulphonic acid condensed with formaldehyde; sodium salt of condensed sulfonated naphtalene;
perfluoroalkylsulfonic acid;
10007] In some exemplary embodiments, the organic active compounds are included in at least one of the sizing composition and the binder composition, [0008] In some exemplary embodiments, the organic active compounds comprise one or more of sulphosuccinate (di-octyl); polyvinylalcohol; colloidal silica;
polyacrylamide;
phosphonic acid; polyacrylic acid, such as polycarboxylate and anionic polyelectolyte;
phosphate ester; polycarboxylic acid, such as acrylic, maleic, lactic, tartaric, etc.; polymeric anionic compounds, such as polyvinylsulphonic acid and poly(meth)acrylic acid;
hexamethylenediaminetetralds; chitin; chitosan; inulin; polyaspartic acid;
polysuccinimide;
iminodisuccinate; maleic acid/acrylic acid copolymer; maleic acid/acrylamide copolymer;
humic acid; calcium salt of polymers from naphtalenenesulphonic acid condensed with formaldehyde; sodium salt of condensed sulfonated naphtalene;
perfluoroallcylsulfonic acid;
and cellulose.
[0009] Various aspects of the general inventive concepts are directed to a lead-acid battery that includes at least one positive electrode and at least one negative electrode immersed within an electrolyte and a non-woven glass fiber pasting mat at least partially covering a surface of at least one of the positive and negative electrode. The non-woven fiber pasting mat includes a plurality of glass fibers coated with a sizing composition, a binder composition, and one or more organic active compounds.
In some exemplary embodiments, the organic active compounds reduce formation of lead sulphate on said negative electrode.
[0010] In some exemplary embodiments, said organic active compounds are included in at least one of the sizing composition and the binder composition.
[0011] Various exemplary embodiments of the general inventive concepts are further directed to a method of forming an anti-sulphation pasting mat for use in a lead-acid battery. The method includes dispersing a plurality of glass fibers into an aqueous slurry, said glass fibers being coated with a sizing composition;
depositing the slurry onto a moving screen; applying a binder onto the deposited slurry; and heating the binder-coated slurry, thereby curing the binder and forming a non-woven pasting mat. The pasting mat includes one or more organic active compounds included in at least one of the sizing composition and the binder.
[0012] In some exemplary embodiments, the non-woven fiber pasting mat is capable of increasing the life cycle of a lead-acid battery by at least 10% compared to an otherwise comparable battery without the pasting mat.
10012a] In one aspect, there is provided a non-woven fiber pasting mat comprising: a plurality of fibers coated with a sizing composition, wherein the sizing composition is coated on the plurality of fibers by a process that includes applying an aqueous-based suspension or emulsion comprising a film former selected from a group consisting of polyvinyl acetates, polyurethanes, modified polyolefins, polyesters epoxides, and mixtures thereof, to the plurality of fibers; a binder composition applied onto the coated fibers, wherein the binder composition is different from the sizing composition; and one or more organic active compounds included in at least one of said sizing composition and said binder composition, said organic active compounds comprising one or more of di-octyl sulphosuccinate;
polyvinylalcohol; colloidal silica;
polyacrylamide; phosphonic acid; polyacrylic acid; phosphate ester;
polycarboxylic acid; polymeric anionic compounds; hexamethylenediaminetetrakis-(methylenephosphonic acid); chitin;
chitosan; mull;
polyaspartic acid; polysuccinimide; iminodisuccinate; maleic acid/acrylic acid copolymer; maleic acid/acrylamide copolymer; humic acid; calcium salt of polymers from naphtalenenesulphonic acid condensed with formaldehyde; sodium salt of condensed sulfonated naphtalene;
perfluoroalkylsulfonic acid; and cellulose, wherein the binder composition holds the fibers together to form said non-woven mat, and wherein said one or more organic active compounds operate to reduce sulphation in a lead-acid battery.
Date Recue/Date Received 2022-06-22 [0012b] In another aspect, there is provided a lead-acid battery comprising: a positive electrode having a first face and a second face opposite said first face and a negative electrode having a first face and a second face opposite said first face, wherein each of said positive and negative electrode is immersed within an electrolyte; a non-woven fiber pasting mat at least partially covering a surface of at least one of said first and second faces of at least one of said positive and said negative electrode, said non-woven fiber pasting mat comprising: a plurality of fibers coated with a sizing composition, wherein the sizing composition is coated on the plurality of fibers by a process that includes applying an aqueous-based suspension or emulsion comprising a film former selected from a group consisting of polyvinyl acetates, polyurethanes, modified polyolefins, polyesters epoxides, and mixtures thereof, to the plurality of fibers; a binder composition applied onto the coated fibers; wherein the binder composition is different from the sizing composition; and one or more organic active compounds included in at least one of said sizing composition and said binder composition, said organic active compounds comprising one or more of di-octyl sulphosuccinate; polyvinylalcohol; colloidal silica; polyacrylamide;
phosphonic acid; polyacrylic acid;
phosphate ester; polycarboxylic acid; polymeric anionic compounds;
hexamethylenediaminetetrakis-(methylenephosphonic acid); chitin; chitosan; inulin; polyaspartic acid;
polysuccinimide; iminodisuccinate;
maleic acid/acrylic acid copolymer; maleic acid/acrylamide copolymer; humic acid; calcium salt of polymers from naphtalenenesulphonic acid condensed with formaldehyde; sodium salt of condensed sulfonated naphtalene; perfluoroalkylsulfonic acid; and cellulose, wherein the binder composition holds the fibers together to form the non-woven fiber pasting mat, and wherein said one or more organic active compounds operate to reduce sulphation in the lead-acid battery.
[0012c1 In another aspect, there is provided a method of forming a non-woven fiber mat for use in a lead-acid battery, said method comprising: dispersing a plurality of fibers into an aqueous slurry, said fibers being coated with a sizing composition, wherein the sizing composition is an aqueous based suspension or emulsion comprising a film former selected from a group consisting of polyvinyl acetates, polyurethanes, modified polyolefins, polyesters epoxides, and mixtures thereof; depositing said slurry onto a screen;
applying a binder onto the fibers of the deposited slurry, wherein the binder is different from the sizing composition; and heating said deposited slurry, thereby curing said binder on the fibers of the deposited slurry and forming said non-woven fiber mat, wherein said fiber mat includes one or more organic active compounds included in at least one of said sizing composition and said binder, said organic active compounds comprising one or more of di-octyl sulphosuccinate;
polyvinylalcohol; colloidal silica;
polyacrylamide; phosphonic acid; polyacrylic acid; phosphate ester;
polycarboxylic acid; polymeric anionic compounds; hexamethylenediaminetetrakis-(methylenephosphonic acid); chitin;
chitosan; inulin;
polyaspartic acid; polysuccinimide; iminodisuccinate; maleic acid/acrylic acid copolymer; maleic acid/
Date Regue/Date Received 2022-10-26 acrylamide copolymer; humic acid; calcium salt of polymers from naphtalenenesulphonic acid condensed with formaldehyde; sodium salt of condensed sulfonated naphtalene;
perfluoroalkylsulfonic acid; and cellulose.
10012d] In another aspect, there is provided a non-woven retainer mat for contacting a separator in a lead-acid battery comprising: a plurality of fibers coated with a sizing composition, wherein the sizing composition is coated on the plurality of fibers by a process that includes applying an aqueous-based suspension or emulsion comprising a film former selected from a group consisting of polyvinyl acetates, polyurethanes, modified polyokfins, polyesters epoxides, and mixtures thereof, to the plurality of fibers; a binder composition applied onto the coated fibers, wherein the binder composition is different from the sizing composition; and one or more additives included in at least one of said sizing composition and said binder composition, said one or more additives comprising one or more of di-octyl sulphosuccinate;
polyvinylakohol; colloidal silica; polyacrylamide; phosphonic acid;
polyacrylic acid; phosphate ester;
polycarboxylic acid; polymeric anionic compounds; hexamethylenediaminetetrakis-(methylenephosphonic acid); chitin; chitosan; inulin; polyaspartic acid; polysuccinimide;
iminodisuccinate; maleic acid/acrylic acid copolymer; maleic acid/acrylamide copolymer; humic acid; calcium salt of polymers from naphtalenenesulphonic acid condensed with formaldehyde; sodium salt of condensed sulfonated naphtalene; perfluoroalkylsulfonic acid; rubber additives; rubber derivatives;
aldehydes; aldehyde derivatives; metals salts; fatty alcohol ethyloxylates; ethylene-propylene oxide block copolymers; sulphate esters; sulphonate esters; sulphosuccinates; lignin; lignin derivatives;
phenol formaldehyde resin; wood flour; and cellulose, wherein the binder composition holds the fibers together to form the non-woven retainer mat, and wherein said one or more additives operate to reduce sulphation in the lead-acid battery.
[0012e1 In another aspect, there is provided a lead-acid battery comprising: a positive electrode, a negative electrode, and a separator, having a first face and a second face opposite thereto, disposed therebetween, wherein each of the positive electrode negative electrode, and separator is immersed within an electrolyte;
and the non-woven retainer mat described herein.
100131 Additional features and advantages will be set forth in part in the description that follows, and in part may be obvious from the description, or may be learned by practice of the exemplary embodiments disclosed herein. It is to be understood that both the foregoing summary and the following detailed description are explanatory only and are not restrictive of the general inventive concepts as disclosed herein or as claimed.
4a Date Recue/Date Received 2022-06-22 DESCRIPTION OF THE DRAWINGS
[0014] Example embodiments of the invention will be apparent from the more particular description of certain example embodiments of the invention provided below and as illustrated in the accompanying drawings.
[0015] Figure 1 graphically illustrates the electrical resistance normalized over 0.10 mm thickness for exemplary non-woven fiber mats prepared in accordance with the present invention.
DETAILED DESCRIPTION
[0016] Various exemplary embodiments will now be described more fully, with occasional reference to any accompanying drawings. These exemplary embodiments may, however, be embodied in different forms and should not be construed as limited to the descriptions set forth herein.
Rather, these exemplary embodiments are provided so that this disclosure will be thorough and complete, and will convey the general inventive concepts to those skilled in the art.
[0017] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which these exemplary embodiments belong.
The terminology used in the description herein is for describing particular exemplary embodiments only and is not intended to be limiting of the exemplary embodiments.
[0018] As used in the specification and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
[0019] Unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about" Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present exemplary embodiments. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should be construed in light of the number of significant digits and ordinary rounding approaches.
[0020] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the exemplary embodiments are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. Every numerical range given throughout this specification and claims will include every narrower numerical range that falls within such 4b Date Recue/Date Received 2022-06-22 broader numerical range, as if such narrower numerical ranges were all expressly written herein.
[0021] The general inventive concepts relate to a non-woven fiber mat, such as a pasting mat or a retainer mat, or other batteries. The non-woven fiber mat may comprise a plurality of reinforcement fibers combined in the form of a sheet. In some exemplary embodiments, the reinforcement fibers are made from glass. However, the reinforcement fibers may also include synthetic fibers, or a combination of glass fibers and synthetic fibers. The term synthetic fiber, as used herein, is intended to include any man-made fiber having suitable reinforcing characteristics including fibers made from suitable polymers such as, for example, polyesters, polyolefins, nylons, aramids, poly(phenylene sulfide), and suitable non-glass fibers such as, carbon, silicon carbide (SiC) and boron nitride.
100221 The glass fibers may be formed from any type of glass suitable for a particular application and/or desired product specifications, including conventional glasses. Non-exclusive examples of glass fibers include A-type glass fibers, C-type glass fibers, G-type glass fiber, E-type glass fibers, S-type glass fibers, E-CR-type glass fibers (e.g., Advantexe glass fibers commercially available from Owens Corning), R-type glass fibers, wool glass fibers, biosoluble glass fibers, and combinations thereof, which may be used as the reinforcing fiber. In some exemplary embodiments, the glass fibers are durable in an acidic environment.
[0023] The non-woven glass fiber mat may comprise a single mat, or more than one mat, e.g., two, three, four, or five mats, which may be employed in a single lead-acid battery. Each non-woven glass fiber mat may comprise a single layer, or may be composed of more than one layer, e.g., two, three, four, or five layers. In some exemplary embodiments, the non-woven fiber mat comprises a non-woven glass fiber pasting mat. In some exemplary embodiments, the non-woven fiber mat comprises a non-woven glass fiber retainer mat.
[0024] In some exemplary embodiments, the glass fibers have a diameter that is at least 0.2 microns, such as from 0.2 to 30 microns. In some exemplary embodiments, the glass fibers have a diameter from about 1 to about 25 microns, or from about 6 to about 23 microns.
100251 Glass fibers may be formed by drawing molten glass into filaments through a bushing or orifice plate and applying a sizing composition to the filaments as they solidify. The sizing composition provides protection to the fibers from interfilament abrasion and promotes compatibility between the glass fibers and the matrix in which the glass fibers are to be used.
After the sizing composition is applied, the fibers may be gathered into one or more strands and wound into a package or, alternatively, the fibers may be chopped while wet with the sizing and collected. The collected chopped strands may then be dried to form dry chopped fibers or they can be packaged in their wet condition as wet chopped fibers.
100261 In some exemplary embodiments, the sizing compositions used to coat glass fibers are aqueous-based compositions, such as suspensions or emulsions. The suspension or emulsion has a solids content that may be composed of one or more of a film former, a coupling agent, a lubricant, and a surfactant. A film former may work to hold individual filaments together to form fibers, and protect the filaments from damage caused by abrasion.
Acceptable film formers include, for example, polyvinyl acetates, polyurethanes, modified polyolefins, polyesters epoxides, and mixtures thereof A coupling agent may be included in a sizing composition to enhance the adhesion of the sizing composition with a matrix material when forming a composite, to improve the composite properties. In some exemplary embodiments, the coupling agent is an organofunctional silane.
10027] Additional additives may be included in the sizing compositions, depending on the intended application. Such additives include, for example, anti-statics, wetting agents, antioxidants, and pH modifiers.
100281 In accordance with the general inventive concepts, the non-woven glass fiber mat may be produced using either continuous or chopped fibers, or a combination of the continuous and chopped fibers. The chopped fibers or fiber strands have lengths that may vary depending on a particular process and/or application. In some exemplary embodiments, the chopped fibers/strands have a length of about 3 to about 60 mm.
10029] The non-woven glass fiber mats may be formed in accordance with any of the known methods for producing glass fiber mats, such as wet-laid processing and dry-laid processing.
In a wet-laid processing, a water slurry (i.e., "whitewater") is provided into which glass fibers are dispersed. The white water may contain dispersants, viscosity modifiers, defoaming agents or other chemical agents. The slurry containing the glass fibers is then deposited onto a moving screen and a substantial amount of the water is removed. A binder may then be applied to the deposited fibers and the resulting mat is dried to remove any remaining water and to cure the binder, forming a non-woven glass fiber mat. In a dry-laid process, fibers are chopped and air blown onto a conveyor and a binder is then applied to form a mat. Dry-laid processes may be particularly suitable for the production of highly porous mats having bundles of glass fibers.
[0030] The binder may be any type of binder composition, such as an acrylic binder, a styrene acrylonitrile binder, a styrene butadiene rubber binder, a urea formaldehyde binder, an epoxy binder, a polyurethane binder, a phenolic binder, a polyester binder, or mixtures thereof. Exemplary acrylic binders may include, for example, polyacrylic acid, ethylacrylate, methacrylate, methylmethacrylate, styrene acrylate, or mixtures thereof. In some exemplary embodiments, the binder is a thermoset acrylic binder formed of polyacrylic acid and at least one polyol, such as for example, triethanolamine or glycerine. The binder may optionally contain one or more additives for improving processibility and/or product performance. Non-limiting examples of such additives include dyes, oils, fillers, colorants, UV
stabilizers, coupling agents (for example, aminosilanes), lubricants, wetting agents, surfactants, antistatic agents, and combinations thereof.
100311 In some exemplary embodiments, the binder comprises about 1 to about 30 weight percent of the total dry weight of the glass fiber mat. In other exemplary embodiments, the binder comprises about 8 to about 25 weight percent of the total dry weight of the glass fiber mat. In some exemplary embodiments, the binder comprises about 18 to 25 weight percent of the total dry weight of the glass fiber mat.
[0032] In some exemplary embodiments, the non-woven glass fiber mats are treated with one or more organic active compounds that are capable of reducing or eliminating sulphation of the electrodes in a lead-acid battery. The organic active compounds may be included as additives to the sizing composition, additives to the binder composition, or as an additive to both the sizing and binder compositions. In some exemplary embodiments, the additives may be added to the surface of the mat, after the mat has been formed.
[0033] In some exemplary embodiments, the organic active compounds include active ingredients that directly influence the reactions that take place on the surface of an electrode.
In some exemplary embodiments, the organic active compounds include one or more of sulphosuccinate (di-octyl); polyvinylalcohol; colloidal silica;
polyacrylamide; phosphonic acid; polyacrylic acid, such as polycarboxylate and anionic polyelectolyte;
phosphate ester;
polycarboxylic acid, such as acrylic, maleic, lactic, tartaric, etc.;
polymeric anionic compounds, such as polyvinylsulphonic acid and poly(meth)acrylic acid;
hexamethylenediaminetetrakis; chitin; chitosan;
polyaspartic acid; polysuccinimide;
iminodisuccinate; maleic acid/acrylic acid copolymer; maleic acid/acrylamide copolymer;
humic acid; calcium salt of polymers from naphtalenenesulphonic acid condensed with formaldehyde; sodium salt of condensed sulfonated naphtalene;
perfluoroalkylsulfonic acid;
7 and cellulose. In some exemplary embodiments, the organic active ingredients include one or more of sulphosuccinate (di-octyl) and a polyvinylalcohol/colloidal silica compound.
[0034] The organic active compounds are capable of reacting directly with lead sulfate that forms during discharge of a lead-acid battery. Sulphation is primarily an issue on the negative plates, where sulphation deteriorates the negative electrode properties. By reacting with the lead sulfate, the organic active compounds keep the lead sulfate soluble in the sulfuric acid electrolyte, which may at least delay, and in some cases inhibit or otherwise reduce, the formation of lead sulfate crystals. In some exemplary embodiments, the use of organic active compounds as described herein prevents the formation of lead sulfate crystals.
[0035] In some exemplary embodiments, the organic active compounds are present in the non-woven mat in an amount from about 0.05 to about 25.0 weight percent of said binder and/or sizing composition containing the organic compounds. In other exemplary embodiments, said organic active compounds are present in an amount from about 0.1 to about 20 weight percent of said binder or sizing composition containing the organic active compounds.
[0036] In some exemplary embodiments, the binder itself may act as an anti-sulphation composition. For example, a polyacrylic acid binder may also react directly with the lead sulphate to maintain its solubility in the electrolyte. Accordingly, in some exemplary embodiments, 100% (or substantially all) of the binder will comprise surface active chemistry.
[0037] By incorporating the organic active compounds directly into the sizing composition and/or into the binder composition, the organic active compounds are directly exposed to the surface of the electrodes where lead sulphate crystals form. The organic active compounds have a limited solubility in the acid electrolyte and are released slowly during use once the non-woven mat is in the acid electrolyte and the plates become active.
Utilizing the non-woven fiber mat as a pasting mat allows for thehe slow release of the organic active compounds from the pasting mat allows the organic active compounds to achieve direct contact with the surface of the electrodes. The solubility of the organic active compounds in the acid electrolyte may be affected by the temperature, as fairly high temperatures are reached in battery curing and formation. The high temperatures may initiate leaching from the pasting mat to the surface of the negative electrode.
[0038] The organic active compounds are prone to oxidation, which is undesirable as oxidation may destroy their anti-sulphation activity and their oxidation products may be
[0034] The organic active compounds are capable of reacting directly with lead sulfate that forms during discharge of a lead-acid battery. Sulphation is primarily an issue on the negative plates, where sulphation deteriorates the negative electrode properties. By reacting with the lead sulfate, the organic active compounds keep the lead sulfate soluble in the sulfuric acid electrolyte, which may at least delay, and in some cases inhibit or otherwise reduce, the formation of lead sulfate crystals. In some exemplary embodiments, the use of organic active compounds as described herein prevents the formation of lead sulfate crystals.
[0035] In some exemplary embodiments, the organic active compounds are present in the non-woven mat in an amount from about 0.05 to about 25.0 weight percent of said binder and/or sizing composition containing the organic compounds. In other exemplary embodiments, said organic active compounds are present in an amount from about 0.1 to about 20 weight percent of said binder or sizing composition containing the organic active compounds.
[0036] In some exemplary embodiments, the binder itself may act as an anti-sulphation composition. For example, a polyacrylic acid binder may also react directly with the lead sulphate to maintain its solubility in the electrolyte. Accordingly, in some exemplary embodiments, 100% (or substantially all) of the binder will comprise surface active chemistry.
[0037] By incorporating the organic active compounds directly into the sizing composition and/or into the binder composition, the organic active compounds are directly exposed to the surface of the electrodes where lead sulphate crystals form. The organic active compounds have a limited solubility in the acid electrolyte and are released slowly during use once the non-woven mat is in the acid electrolyte and the plates become active.
Utilizing the non-woven fiber mat as a pasting mat allows for thehe slow release of the organic active compounds from the pasting mat allows the organic active compounds to achieve direct contact with the surface of the electrodes. The solubility of the organic active compounds in the acid electrolyte may be affected by the temperature, as fairly high temperatures are reached in battery curing and formation. The high temperatures may initiate leaching from the pasting mat to the surface of the negative electrode.
[0038] The organic active compounds are prone to oxidation, which is undesirable as oxidation may destroy their anti-sulphation activity and their oxidation products may be
8 harmful for the battery. Oxidation of the organic active compounds mainly takes place at the positive plate because lead dioxide (Pb02) is a very strong oxidizer, especially in combination with sulphuric acid. By applying the organic active compounds to the negative plate via the non-woven pasting mat, the distance to the positive plate is maximized and the organic active compounds have a lower risk of oxidation at the positive plate compared to applications that introduce chemistries directly into the electrolyte.
100391 In some exemplary embodiments, treating the electrode surface with organic active compounds by incorporating one or more organic active compounds into the, sizing composition and/or binder composition of a pasting mat demonstrates an improvement in battery life cycle of at least 10%, or at least about 25% over otherwise similar lead-acid battery cells that either have no pasting mat or include a cellulose base pasting mat.
100401 The process of preparing a lead-acid battery comprises forming one or more battery cells, which each include a positive plate electrode having a first face and a second face, opposite the first face, a negative plate electrode having a first face and a second face, opposite the first face, and a separator disposed therebetvveen. The positive electrode includes a grid containing lead alloy material. A positive active material, such as lead dioxide, is coated on the grid of the positive electrode. The negative plate electrode also includes a grid of lead alloy material that is coated with a negative active material, such as lead. The positive and negative plate electrodes are immersed in an electrolyte that may include sulfuric acid and water. The separator may be positioned between the positive and negative plate electrodes to physically separate the two electrodes while enabling ionic transport.
100411 The non-woven fiber pasting mat disclosed herein may be positioned to partially or fully cover at least one surface of the negative plate electrode. In some exemplary embodiments, pasting mats are positioned on each side of the negative plate electrode. In some exemplary embodiments, the use of glass fibers in the non-woven pasting mat provides added dimensional stability to the negative plates during charge and discharge. During discharge the negative plates generally increase in volume and then shrink significantly during a charging cycle, due to the different crystals formed. The improved dimensional stability provided by the glass fiber pasting mat reduces this expansion/shrinkage, which in turn leads to an improved battery life by preventing active mass from shedding from the grid and maintaining good contact between the active material and the grid to ensure charge acceptance and current flow. In some exemplary embodiments, a non-woven fiber pasting mat is positioned to partially or fully cover at least one surface of the positive plate, to
100391 In some exemplary embodiments, treating the electrode surface with organic active compounds by incorporating one or more organic active compounds into the, sizing composition and/or binder composition of a pasting mat demonstrates an improvement in battery life cycle of at least 10%, or at least about 25% over otherwise similar lead-acid battery cells that either have no pasting mat or include a cellulose base pasting mat.
100401 The process of preparing a lead-acid battery comprises forming one or more battery cells, which each include a positive plate electrode having a first face and a second face, opposite the first face, a negative plate electrode having a first face and a second face, opposite the first face, and a separator disposed therebetvveen. The positive electrode includes a grid containing lead alloy material. A positive active material, such as lead dioxide, is coated on the grid of the positive electrode. The negative plate electrode also includes a grid of lead alloy material that is coated with a negative active material, such as lead. The positive and negative plate electrodes are immersed in an electrolyte that may include sulfuric acid and water. The separator may be positioned between the positive and negative plate electrodes to physically separate the two electrodes while enabling ionic transport.
100411 The non-woven fiber pasting mat disclosed herein may be positioned to partially or fully cover at least one surface of the negative plate electrode. In some exemplary embodiments, pasting mats are positioned on each side of the negative plate electrode. In some exemplary embodiments, the use of glass fibers in the non-woven pasting mat provides added dimensional stability to the negative plates during charge and discharge. During discharge the negative plates generally increase in volume and then shrink significantly during a charging cycle, due to the different crystals formed. The improved dimensional stability provided by the glass fiber pasting mat reduces this expansion/shrinkage, which in turn leads to an improved battery life by preventing active mass from shedding from the grid and maintaining good contact between the active material and the grid to ensure charge acceptance and current flow. In some exemplary embodiments, a non-woven fiber pasting mat is positioned to partially or fully cover at least one surface of the positive plate, to
9 function as a retainer by holding the active material in place on the positive plate while also providing improved dimensional stability. In some exemplary embodiments, pasting mats are positioned on each side of the positive plate electrode. In some exemplary embodiments, non-woven fiber pasting mats are positioned on both sides of each of the positive and negative plates.
[0042] In other exemplary embodiments, the non-woven fiber mat functions as a retainer mat and is positioned in contact with at least one side of the separator.
[0043] The following examples are meant to better illustrate the present invention but are not intended to limit the general inventive concepts in any way.
EXAMPLE
Example 1:
[0044] A variety of 20 hour rate 2 Volt battery cells were assembled and the negative plates were joined with non-woven glass fiber pasting mats having different binder and/or fiber compositions. The cells were then subjected to partial state of charge cycling tests and afterwards submitted to teardown analysis. The presence of crystallized lead sulfate was determined on the top and the bottom of the plate with wet analysis and x-ray diffraction.
A) Partial State of Charge (PSoC) testing method:
[0045] The partial state of charge cycle testing procedure repeats a partial discharge and charge to an amount of capacity around various levels of the average state of charge. An equalization step in the PSoC test method was omitted to increase the partial state of charge residence time and to increase the test speed. The battery cells were subjected to cycling at 17.5% Depth of Discharge (DoD) at 27 C with an initial point of cycling at 50% State of Charge (SoC). The cycling conditions included preconditioning by discharge for 2.5 hours at 4 x 120A (4A), reaching the initial point of cycling at 50% SoC. The batteries were then charged for 40 minutes at Imax=7A (7 x I20A) and Um. = 2.4V/Cell. The batteries were then discharged for 30 minutes at 7A (7 x I20A). The consecutive charge and discharge constituted one cycle. The higher number of cycles indicates a longer battery life time.
After reaching the switch-off criteria (Uceli S 1.666V), the cycling ended and the cell was charged and submitted to a detailed tear down analysis.
B) Tear-Down Analysis:
[0046] To perform the tear down analysis, the negative plate was divided into three sections:
top, middle, and bottom. The active material from the top and bottom of the plate was separately selected at different places and grinded to homogenize the sample.
[0047] The same homogenized sample of top and bottom negative plate active material was used to record an X-ray diffraction pattern. The device used to record the X-ray diffraction pattern was a Philips 2134, ADP-15.
100481 The active material on the top and bottom sections was further analyzed for PbSO4 and Pb content from the final recharge. The PbSO4 weight percent is considered irreversible lead sulphate, indicative of sulphation. Additionally, if the battery has suffered from sulphation, the PbSO4 would be concentrated on the bottom of the plate.
Table 1: Battery Sulphation Sample Organic active 4 of cycles PbSO4 PbSO4 located Comments chemistry at PSoC located at top at bottom of cycling of negative negative plate plate after after final final recharge.
recharge. (wt. %) (wt. %) Comp. None 271 11 % 65 % Commercially Sample 1 available glass pasting mat (acrylic bound glass tissue), strong sulphation Comp. None 410 21% 57% Conductive Sample 2 carbon fiber added, strong sulphation Sample 3 Sulphosuccinate 874 5% 18% Low sulphation (di-octyl) Sample 4 Polyvinylalcohol 579 9% 11% Low sulphation /colloidal silica 100491 As illustrated in Table 1, comparative samples 1 and 2, which included conventional pasting mats without organic active compounds, demonstrated significant sulphation at the bottom of the negative plate. Comparatively, Examples 3 and 4, including organic active compounds, demonstrated significantly lower sulphation of less than 10% and also increased partial state of charge cycling to greater than 500 cycles, which is indicative of a higher battery life.
[0050] Specifically, Sample 3 included a 25 g/m2 pasting mat comprising a mixture of 6.5 gm - 6 mm and 11 gm - 13 mm chopped glass fibers. The mat was bonded with a self-crosslinkable acrylic based binder. The mat had a binder content of about 20%.
A di-ll octylsulphosuccinate surfactant was added to the binder in about 0.2 weight percent based on dry binder solids. Example 4 included a 45 g/m2 pasting mat comprising a base tissue formed of a 50/50 mixture of 6.5 gm - 6 mm glass fibers and 11 gm - 6 mm glass fibers and included about 16 weight percent of a polyvinylalcohol binder. The base sheet was treated with a mixture of self cross-linkable acrylate and colloidal silica. The final mat included about 3g/m2polyvinylalcohol and 22 g/m2 colloidal silica.
Example 2 [0051] A variety of non-woven fiber pasting mats were prepared to have various fiber types, weights, and thicknesses. Table 2 below illustrates the properties of the mats.
Table 2: Properties of Fiber Mats Sample Fiber Weight ' Thickness Air LOI Electrical ER/0.1 type (grams/m2) (mm) permeability measured Resistance mm (vm2s) (%) 1 glass 25.1 0.19 7420 12.0 11.7 ' 6.17 2 glass 22.9 0.205 6780 21.1 13.7 6.66 3 glass 24.6 0.22 8330 16.5 16.3 7.43 4 glass 24.2 - 0,165 ' 5190 18.9 14.1 ' 8.53 glass 131.5 0.9 2400 14.1 37.8 4.20 6 glass 105.3 ' 0.95 4420 15.7 27:1 2.85 7 glass 117.3 0.84 2400 14.7 36.7 4.36 _ 8 glass 23.8 0.19 6930 23.0 13.8 7.24 _ .
9 glass 23.5 0.2 7650 11.9 12.0 6.02 glass 84.5 0.61 3130 15.9 26.0 4.26 11 glass 53.8 0.42 4020 17.8 30.1 7.16 12 glass 39.7 0.33 5130 18.9 23.1 7.01 12 glass 69.1 0.38 1790 18.2 26.0 6.85 _ .
13 ' glass 48.2 - 0.42 4246 11.6 19.6 4.66 14 glass 41.8 0.4 4488 18.8 15.4 3.84 glass 47.5 0.42 4114 ' 27.9 24.3 5.78 _ 16 glass ' 51 0.42 ' -3982 -33.5 46.2 11.01 17 glass 40.3 0.41 5104 16.9 14.2 3.46 18 glass 43.7 0.41 - 4378 19.4 14.0 3.41 19 glass 43.6 0.41 3740 - 20.1 22,0 5,37 ' glass 50.1 0.41 1606 19.8 21.8 5.33 21 glass 39.6 0.4 5786 15.4 7.7 1.94 Comparative polyester 25 0.06 1570 100.0 26.9 44.77 Example-1 Comparative Polyester 18.5 0.08 ' 2850 100.0 19.7 24.59 Example-2 Comparative glass 19.5 0.17 5540 38.0 26.1 15.37 Example -3 [0052] As illustrated in Table 2, the electrical resistance for the non-woven fiber mats was lowest for glass fiber mats prepared in accordance with the present invention.
The electrical resistance, when normalized over 0.10 mm thickness, is lowest for the non-woven glass fiber mats prepared in accordance with the present invention, Each of samples 1-21 demonstrates electrical resistance, normalized over 0.1 mm, of lower than 15/0.1 mm. In some exemplary embodiments, the glass fibers may have an electrical resistance of less than
[0042] In other exemplary embodiments, the non-woven fiber mat functions as a retainer mat and is positioned in contact with at least one side of the separator.
[0043] The following examples are meant to better illustrate the present invention but are not intended to limit the general inventive concepts in any way.
EXAMPLE
Example 1:
[0044] A variety of 20 hour rate 2 Volt battery cells were assembled and the negative plates were joined with non-woven glass fiber pasting mats having different binder and/or fiber compositions. The cells were then subjected to partial state of charge cycling tests and afterwards submitted to teardown analysis. The presence of crystallized lead sulfate was determined on the top and the bottom of the plate with wet analysis and x-ray diffraction.
A) Partial State of Charge (PSoC) testing method:
[0045] The partial state of charge cycle testing procedure repeats a partial discharge and charge to an amount of capacity around various levels of the average state of charge. An equalization step in the PSoC test method was omitted to increase the partial state of charge residence time and to increase the test speed. The battery cells were subjected to cycling at 17.5% Depth of Discharge (DoD) at 27 C with an initial point of cycling at 50% State of Charge (SoC). The cycling conditions included preconditioning by discharge for 2.5 hours at 4 x 120A (4A), reaching the initial point of cycling at 50% SoC. The batteries were then charged for 40 minutes at Imax=7A (7 x I20A) and Um. = 2.4V/Cell. The batteries were then discharged for 30 minutes at 7A (7 x I20A). The consecutive charge and discharge constituted one cycle. The higher number of cycles indicates a longer battery life time.
After reaching the switch-off criteria (Uceli S 1.666V), the cycling ended and the cell was charged and submitted to a detailed tear down analysis.
B) Tear-Down Analysis:
[0046] To perform the tear down analysis, the negative plate was divided into three sections:
top, middle, and bottom. The active material from the top and bottom of the plate was separately selected at different places and grinded to homogenize the sample.
[0047] The same homogenized sample of top and bottom negative plate active material was used to record an X-ray diffraction pattern. The device used to record the X-ray diffraction pattern was a Philips 2134, ADP-15.
100481 The active material on the top and bottom sections was further analyzed for PbSO4 and Pb content from the final recharge. The PbSO4 weight percent is considered irreversible lead sulphate, indicative of sulphation. Additionally, if the battery has suffered from sulphation, the PbSO4 would be concentrated on the bottom of the plate.
Table 1: Battery Sulphation Sample Organic active 4 of cycles PbSO4 PbSO4 located Comments chemistry at PSoC located at top at bottom of cycling of negative negative plate plate after after final final recharge.
recharge. (wt. %) (wt. %) Comp. None 271 11 % 65 % Commercially Sample 1 available glass pasting mat (acrylic bound glass tissue), strong sulphation Comp. None 410 21% 57% Conductive Sample 2 carbon fiber added, strong sulphation Sample 3 Sulphosuccinate 874 5% 18% Low sulphation (di-octyl) Sample 4 Polyvinylalcohol 579 9% 11% Low sulphation /colloidal silica 100491 As illustrated in Table 1, comparative samples 1 and 2, which included conventional pasting mats without organic active compounds, demonstrated significant sulphation at the bottom of the negative plate. Comparatively, Examples 3 and 4, including organic active compounds, demonstrated significantly lower sulphation of less than 10% and also increased partial state of charge cycling to greater than 500 cycles, which is indicative of a higher battery life.
[0050] Specifically, Sample 3 included a 25 g/m2 pasting mat comprising a mixture of 6.5 gm - 6 mm and 11 gm - 13 mm chopped glass fibers. The mat was bonded with a self-crosslinkable acrylic based binder. The mat had a binder content of about 20%.
A di-ll octylsulphosuccinate surfactant was added to the binder in about 0.2 weight percent based on dry binder solids. Example 4 included a 45 g/m2 pasting mat comprising a base tissue formed of a 50/50 mixture of 6.5 gm - 6 mm glass fibers and 11 gm - 6 mm glass fibers and included about 16 weight percent of a polyvinylalcohol binder. The base sheet was treated with a mixture of self cross-linkable acrylate and colloidal silica. The final mat included about 3g/m2polyvinylalcohol and 22 g/m2 colloidal silica.
Example 2 [0051] A variety of non-woven fiber pasting mats were prepared to have various fiber types, weights, and thicknesses. Table 2 below illustrates the properties of the mats.
Table 2: Properties of Fiber Mats Sample Fiber Weight ' Thickness Air LOI Electrical ER/0.1 type (grams/m2) (mm) permeability measured Resistance mm (vm2s) (%) 1 glass 25.1 0.19 7420 12.0 11.7 ' 6.17 2 glass 22.9 0.205 6780 21.1 13.7 6.66 3 glass 24.6 0.22 8330 16.5 16.3 7.43 4 glass 24.2 - 0,165 ' 5190 18.9 14.1 ' 8.53 glass 131.5 0.9 2400 14.1 37.8 4.20 6 glass 105.3 ' 0.95 4420 15.7 27:1 2.85 7 glass 117.3 0.84 2400 14.7 36.7 4.36 _ 8 glass 23.8 0.19 6930 23.0 13.8 7.24 _ .
9 glass 23.5 0.2 7650 11.9 12.0 6.02 glass 84.5 0.61 3130 15.9 26.0 4.26 11 glass 53.8 0.42 4020 17.8 30.1 7.16 12 glass 39.7 0.33 5130 18.9 23.1 7.01 12 glass 69.1 0.38 1790 18.2 26.0 6.85 _ .
13 ' glass 48.2 - 0.42 4246 11.6 19.6 4.66 14 glass 41.8 0.4 4488 18.8 15.4 3.84 glass 47.5 0.42 4114 ' 27.9 24.3 5.78 _ 16 glass ' 51 0.42 ' -3982 -33.5 46.2 11.01 17 glass 40.3 0.41 5104 16.9 14.2 3.46 18 glass 43.7 0.41 - 4378 19.4 14.0 3.41 19 glass 43.6 0.41 3740 - 20.1 22,0 5,37 ' glass 50.1 0.41 1606 19.8 21.8 5.33 21 glass 39.6 0.4 5786 15.4 7.7 1.94 Comparative polyester 25 0.06 1570 100.0 26.9 44.77 Example-1 Comparative Polyester 18.5 0.08 ' 2850 100.0 19.7 24.59 Example-2 Comparative glass 19.5 0.17 5540 38.0 26.1 15.37 Example -3 [0052] As illustrated in Table 2, the electrical resistance for the non-woven fiber mats was lowest for glass fiber mats prepared in accordance with the present invention.
The electrical resistance, when normalized over 0.10 mm thickness, is lowest for the non-woven glass fiber mats prepared in accordance with the present invention, Each of samples 1-21 demonstrates electrical resistance, normalized over 0.1 mm, of lower than 15/0.1 mm. In some exemplary embodiments, the glass fibers may have an electrical resistance of less than
10/0.1 mm. The normalized electrical resistances of the examples illustrated in Table 2 are further compared in Figure 1, which shows that each of the non-woven glass fiber mats formed according to the present invention (0C1-13 and lab examples) demonstrates an electrical resistance normalized over 0.1 mm that is far less than 15.
[0053] Although the general inventive concepts have been set forth in what is believed to be exemplary illustrative embodiments, a wide variety of alternatives would be known or otherwise apparent to those of skill in the art and, thus, are encompassed by the general inventive concepts. The general inventive concepts are not otherwise limited, except for the recitation of the claims set forth below.
[0053] Although the general inventive concepts have been set forth in what is believed to be exemplary illustrative embodiments, a wide variety of alternatives would be known or otherwise apparent to those of skill in the art and, thus, are encompassed by the general inventive concepts. The general inventive concepts are not otherwise limited, except for the recitation of the claims set forth below.
Claims (27)
1. A non-woven fiber pasting mat comprising:
a plurality of fibers coated with a sizing composition, wherein the sizing composition is coated on the plurality of fibers by a process that includes applying an aqueous-based suspension or emulsion comprising a film former selected from a group consisting of polyvinyl acetates, polyurethanes, modified polyolefins, polyesters epoxides, and mixtures thereof, to the plurality of fibers;
a binder composition applied onto the coated fibers, wherein the binder composition is different from the sizing composition; and one or more organic active compounds included in at least one of said sizing composition and said binder composition, said organic active compounds comprising one or more of di-octyl sulphosuccinate;
polyvinylalcohol; colloidal silica; polyacrylamide; phosphonic acid;
polyacrylic acid; phosphate ester;
polycarboxylic acid; polymeric anionic compounds; hexamethylenediaminetetrakis-(methylenephosphonic acid); chitin; chitosan; inulin; polyaspartic acid; polysuccinimide;
iminodisuccinate; maleic acid/acrylic acid copolymer; maleic acid/acrylamide copolymer; humic acid; calcium salt of polymers from naphtalenenesulphonic acid condensed with formaldehyde; sodium salt of condensed sulfonated naphtalene; perfluoroalkylsulfonic acid; and cellulose, wherein the binder composition holds the fibers together to form said non-woven mat, and wherein said one or more organic active compounds operate to reduce sulphation in a lead-acid battery.
a plurality of fibers coated with a sizing composition, wherein the sizing composition is coated on the plurality of fibers by a process that includes applying an aqueous-based suspension or emulsion comprising a film former selected from a group consisting of polyvinyl acetates, polyurethanes, modified polyolefins, polyesters epoxides, and mixtures thereof, to the plurality of fibers;
a binder composition applied onto the coated fibers, wherein the binder composition is different from the sizing composition; and one or more organic active compounds included in at least one of said sizing composition and said binder composition, said organic active compounds comprising one or more of di-octyl sulphosuccinate;
polyvinylalcohol; colloidal silica; polyacrylamide; phosphonic acid;
polyacrylic acid; phosphate ester;
polycarboxylic acid; polymeric anionic compounds; hexamethylenediaminetetrakis-(methylenephosphonic acid); chitin; chitosan; inulin; polyaspartic acid; polysuccinimide;
iminodisuccinate; maleic acid/acrylic acid copolymer; maleic acid/acrylamide copolymer; humic acid; calcium salt of polymers from naphtalenenesulphonic acid condensed with formaldehyde; sodium salt of condensed sulfonated naphtalene; perfluoroalkylsulfonic acid; and cellulose, wherein the binder composition holds the fibers together to form said non-woven mat, and wherein said one or more organic active compounds operate to reduce sulphation in a lead-acid battery.
2. The non-woven fiber pasting mat of claim 1, wherein said binder composition is selected from the group consisting of an acrylic binder, a styrene acrylonitrile binder, a styrene butadiene rubber binder, an epoxy binder, a polyurethane binder, a phenolic binder, a polyester binder, and mixtures thereof.
3. The non-woven fiber pasting mat of claim 1, wherein said binder composition is an acid resistant binder.
4. The non-woven fiber pasting mat of claim 1, wherein said fibers comprise one or more of glass fibers, polyester fibers, polyolefin fibers, nylon fibers, aramid fibers, poly(phenylene sulfide) fibers, carbon fibers, silicon carbide (SiC) fibers, and boron nitride fibers.
5. The non-woven fiber pasting mat of claim 1, wherein said fibers comprise glass fibers.
Date Regue/Date Received 2022-10-26
Date Regue/Date Received 2022-10-26
6. The non-woven fiber pasting mat of claim 1, wherein said fibers have an average diameter of about 0.2 microns to about 30 microns.
7. The non-woven fiber pasting mat of claim 5, wherein said fibers have an average diameter of about 1 micron to about 25 microns.
8. The non-woven fiber pasting mat of claim 1, wherein said fibers are chopped fibers having an average length of between about 3 mm and about 60 mm.
9. The non-woven fiber pasting mat of claim 1, wherein said organic active compounds comprise one or more of di-octyl sulphosuccinate and a compound comprising polyvinylalcohol and colloidal silica.
10. The non-woven fiber pasting mat of claim 1, wherein said non-woven fiber pasting mat operates to increase the life cycle of the lead-acid battery by at least 10%
compared to an otherwise comparable battery without said pasting mat.
compared to an otherwise comparable battery without said pasting mat.
11. The non-woven fiber pasting mat of claim 1, wherein said non-woven fiber pasting mat has an electrical resistance of less than 15 mf1/cm2 per 0.1 mm thickness of the pasting mat.
12. The non-woven fiber pasting mat of claim 1, wherein said fiber pasting mat has an electrical resistance of less than 10 m12/cm2 per 0.1 mm thickness of the pasting mat.
13. A lead-acid battery comprising:
a positive electrode having a first face and a second face opposite said first face and a negative electrode having a first face and a second face opposite said first face, wherein each of said positive and negative electrode is immersed within an electrolyte;
a non-woven fiber pasting mat at least partially covering a surface of at least one of said first and second faces of at least one of said positive and said negative electrode, said non-woven fiber pasting mat comprising:
Date Regue/Date Received 2022-10-26 a plurality of fibers coated with a sizing composition, wherein the sizing composition is coated on the plurality of fibers by a process that includes applying an aqueous-based suspension or emulsion comprising a film former selected from a group consisting of polyvinyl acetates, polyurethanes, modified polyolefins, polyesters epoxides, and mixtures thereof, to the plurality of fibers;
a binder composition applied onto the coated fibers, wherein the binder composition is different from the sizing composition; and one or more organic active compounds included in at least one of said sizing composition and said binder composition, said organic active compounds comprising one or more of di-octyl sulphosuccinate;
polyvinylalcohol; colloidal silica; polyacrylamide; phosphonic acid;
polyacrylic acid; phosphate ester;
polycarboxylic acid; polymeric anionic compounds; hexamethylenediaminetetrakis-(methylenephosphonic acid); chitin; chitosan; inulin; polyaspartic acid; polysuccinimide;
iminodisuccinate; maleic acid/acrylic acid copolymer; maleic acid/acrylamide copolymer; humic acid; calcium salt of polymers from naphtalenenesulphonic acid condensed with formaldehyde; sodium salt of condensed sulfonated naphtalene; perfluoroalkylsulfonic acid; and cellulose, wherein the binder composition holds the fibers together to form the non-woven fiber pasting mat, and wherein said one or more organic active compounds operate to reduce sulphation in the lead-acid battery.
a positive electrode having a first face and a second face opposite said first face and a negative electrode having a first face and a second face opposite said first face, wherein each of said positive and negative electrode is immersed within an electrolyte;
a non-woven fiber pasting mat at least partially covering a surface of at least one of said first and second faces of at least one of said positive and said negative electrode, said non-woven fiber pasting mat comprising:
Date Regue/Date Received 2022-10-26 a plurality of fibers coated with a sizing composition, wherein the sizing composition is coated on the plurality of fibers by a process that includes applying an aqueous-based suspension or emulsion comprising a film former selected from a group consisting of polyvinyl acetates, polyurethanes, modified polyolefins, polyesters epoxides, and mixtures thereof, to the plurality of fibers;
a binder composition applied onto the coated fibers, wherein the binder composition is different from the sizing composition; and one or more organic active compounds included in at least one of said sizing composition and said binder composition, said organic active compounds comprising one or more of di-octyl sulphosuccinate;
polyvinylalcohol; colloidal silica; polyacrylamide; phosphonic acid;
polyacrylic acid; phosphate ester;
polycarboxylic acid; polymeric anionic compounds; hexamethylenediaminetetrakis-(methylenephosphonic acid); chitin; chitosan; inulin; polyaspartic acid; polysuccinimide;
iminodisuccinate; maleic acid/acrylic acid copolymer; maleic acid/acrylamide copolymer; humic acid; calcium salt of polymers from naphtalenenesulphonic acid condensed with formaldehyde; sodium salt of condensed sulfonated naphtalene; perfluoroalkylsulfonic acid; and cellulose, wherein the binder composition holds the fibers together to form the non-woven fiber pasting mat, and wherein said one or more organic active compounds operate to reduce sulphation in the lead-acid battery.
14. The lead-acid battery of claim 13, wherein said fibers comprise one or more of glass fibers, polyester fibers, polyolefin fibers, nylon fibers, aramid fibers, poly(phenylene sulfide) fibers, carbon fibers, silicon carbide (SiC) fibers, and boron nitride fibers.
15. The lead-acid battery of claim 13, wherein said fibers have an average diameter of about 0.2 microns to about 30 microns.
16. The lead-acid battery of claim 15, wherein said fibers have an average diameter of about 1 micron to about 25 microns.
17. The lead-acid battery of claim 13, wherein said fibers are chopped fibers having an average length of between about 3 mm and about 60 mm.
Date Regue/Date Received 2022-10-26
Date Regue/Date Received 2022-10-26
18. The lead-acid battery of claim 13, wherein said organic active compounds comprise one or more of di-octyl sulphosuccinate and a compound comprising polyvinylalcohol and colloidal silica.
19. The lead-acid battery of claim 13, wherein said non-woven fiber pasting mat has an electrical resistance of less than 15 mf2/cm2 per 0.1 mm thickness of the pasting mat.
20. The lead-acid battery of claim 13, wherein the non-woven fiber pasting mat is at least partially covering each of said first and second faces of said positive electrode.
21. The lead-acid battery of claim 13, wherein the non-woven fiber pasting mat is at least partially covering each of said first and second faces of said negative electrode.
22. A method of forming a non-woven fiber mat for use in a lead-acid battery, said method comprising:
dispersing a plurality of fibers into an aqueous sluny, said fibers being coated with a sizing composition, wherein the sizing composition is an aqueous based suspension or emulsion comprising a film former selected from a group consisting of polyvinyl acetates, polyurethanes, modified polyolefins, polyesters epoxides, and mixtures thereof;
depositing said sluny onto a screen;
applying a binder onto the fibers of the deposited sluny, wherein the binder is different from the sizing composition; and heating said deposited slurry, thereby curing said binder on the fibers of the deposited slurry and forming said non-woven fiber mat, wherein said fiber mat includes one or more organic active compounds included in at least one of said sizing composition and said binder, said organic active compounds comprising one or more of di-octyl sulphosuccinate; polyvinylalcohol;
colloidal silica; polyacrylamide;
phosphonic acid; polyacrylic acid; phosphate ester; polycarboxylic acid;
polymeric anionic compounds;
hexamethylenediaminetetrakis-(methylenephosphonic acid); chitin; chitosan;
inulin; polyaspartic acid;
polysuccinimide; iminodisuccinate; maleic acid/acrylic acid copolymer; maleic acid/acrylamide copolymer; humic acid; calcium salt of polymers from naphtalenenesulphonic acid condensed with formaldehyde; sodium salt of condensed sulfonated naphtalene;
perfluoroalkylsulfonic acid; and cellulose.
dispersing a plurality of fibers into an aqueous sluny, said fibers being coated with a sizing composition, wherein the sizing composition is an aqueous based suspension or emulsion comprising a film former selected from a group consisting of polyvinyl acetates, polyurethanes, modified polyolefins, polyesters epoxides, and mixtures thereof;
depositing said sluny onto a screen;
applying a binder onto the fibers of the deposited sluny, wherein the binder is different from the sizing composition; and heating said deposited slurry, thereby curing said binder on the fibers of the deposited slurry and forming said non-woven fiber mat, wherein said fiber mat includes one or more organic active compounds included in at least one of said sizing composition and said binder, said organic active compounds comprising one or more of di-octyl sulphosuccinate; polyvinylalcohol;
colloidal silica; polyacrylamide;
phosphonic acid; polyacrylic acid; phosphate ester; polycarboxylic acid;
polymeric anionic compounds;
hexamethylenediaminetetrakis-(methylenephosphonic acid); chitin; chitosan;
inulin; polyaspartic acid;
polysuccinimide; iminodisuccinate; maleic acid/acrylic acid copolymer; maleic acid/acrylamide copolymer; humic acid; calcium salt of polymers from naphtalenenesulphonic acid condensed with formaldehyde; sodium salt of condensed sulfonated naphtalene;
perfluoroalkylsulfonic acid; and cellulose.
23. A non-woven retainer mat for contacting a separator in a lead-acid battery comprising:
Date Regue/Date Received 2022-10-26 a plurality of fibers coated with a sizing composition, wherein the sizing composition is coated on the plurality of fibers by a process that includes applying an aqueous-based suspension or emulsion comprising a film former selected from a group consisting of polyvinyl acetates, polyurethanes, modified polyolefins, polyesters epoxides, and mixtures thereof, to the plurality of fibers;
a binder composition applied onto the coated fibers, wherein the binder composition is different from the sizing composition; and one or more additives included in at least one of said sizing composition and said binder composition, said one or more additives comprising one or more of di-octyl sulphosuccinate;
polyvinylalcohol; colloidal silica; polyacrylamide; phosphonic acid;
polyacrylic acid; phosphate ester;
polycarboxylic acid; polymeric anionic compounds; hexamethylenediaminetetrakis-(methylenephosphonic acid); chitin; chitosan; inulin; polyaspartic acid; polysuccinimide;
iminodisuccinate; maleic acid/acrylic acid copolymer; maleic acid/acrylamide copolymer; humic acid; calcium salt of polymers from naphtalenenesulphonic acid condensed with formaldehyde; sodium salt of condensed sulfonated naphtalene; perfluoroalkylsulfonic acid; rubber additives; rubber derivatives;
aldehydes; aldehyde derivatives; metals salts; fatty alcohol ethyloxylates; ethylene-propylene oxide block copolymers; sulphate esters; sulphonate esters; sulphosuccinates; lignin; lignin derivatives;
phenol formaldehyde resin; wood flour; and cellulose, wherein the binder composition holds the fibers together to form the non-woven retainer mat, and wherein said one or more additives operate to reduce sulphation in the lead-acid battery.
Date Regue/Date Received 2022-10-26 a plurality of fibers coated with a sizing composition, wherein the sizing composition is coated on the plurality of fibers by a process that includes applying an aqueous-based suspension or emulsion comprising a film former selected from a group consisting of polyvinyl acetates, polyurethanes, modified polyolefins, polyesters epoxides, and mixtures thereof, to the plurality of fibers;
a binder composition applied onto the coated fibers, wherein the binder composition is different from the sizing composition; and one or more additives included in at least one of said sizing composition and said binder composition, said one or more additives comprising one or more of di-octyl sulphosuccinate;
polyvinylalcohol; colloidal silica; polyacrylamide; phosphonic acid;
polyacrylic acid; phosphate ester;
polycarboxylic acid; polymeric anionic compounds; hexamethylenediaminetetrakis-(methylenephosphonic acid); chitin; chitosan; inulin; polyaspartic acid; polysuccinimide;
iminodisuccinate; maleic acid/acrylic acid copolymer; maleic acid/acrylamide copolymer; humic acid; calcium salt of polymers from naphtalenenesulphonic acid condensed with formaldehyde; sodium salt of condensed sulfonated naphtalene; perfluoroalkylsulfonic acid; rubber additives; rubber derivatives;
aldehydes; aldehyde derivatives; metals salts; fatty alcohol ethyloxylates; ethylene-propylene oxide block copolymers; sulphate esters; sulphonate esters; sulphosuccinates; lignin; lignin derivatives;
phenol formaldehyde resin; wood flour; and cellulose, wherein the binder composition holds the fibers together to form the non-woven retainer mat, and wherein said one or more additives operate to reduce sulphation in the lead-acid battery.
24. The non-woven retainer mat of claim 23, wherein said one or more additives comprise about 0.1 weight percent to about 30 weight percent of the non-woven retainer mat.
25. The non-woven retainer mat of claim 23, wherein said additives include one or more of ethylene-propylene oxide block copolymers, aldehydes, polyacrylic acid, and polyaspartic acid.
26. The non-woven retainer mat of claim 23, wherein said non-woven retainer mat operates to increase the life cycle of the lead-acid battery by at least 10% compared to an otherwise comparable lead-acid battery without said non-woven retainer mat.
27. A lead-acid battery comprising:
Date Regue/Date Received 2022-10-26 a positive electrode, a negative electrode, and a separator, having a first face and a second face opposite thereto, disposed therebetween, wherein each of said positive electrode, negative electrode, and separator is immersed within an electrolyte; and the non-woven retainer mat according to claim 23.
Date Regue/Date Received 2022-10-26
Date Regue/Date Received 2022-10-26 a positive electrode, a negative electrode, and a separator, having a first face and a second face opposite thereto, disposed therebetween, wherein each of said positive electrode, negative electrode, and separator is immersed within an electrolyte; and the non-woven retainer mat according to claim 23.
Date Regue/Date Received 2022-10-26
Applications Claiming Priority (3)
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| US201462013097P | 2014-06-17 | 2014-06-17 | |
| US62/013,097 | 2014-06-17 | ||
| PCT/US2015/036142 WO2015195743A1 (en) | 2014-06-17 | 2015-06-17 | Anti-sulphation pasting mats for lead-acid batteries |
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| CA2952434A1 CA2952434A1 (en) | 2015-12-23 |
| CA2952434C true CA2952434C (en) | 2023-08-22 |
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| CA2952434A Active CA2952434C (en) | 2014-06-17 | 2015-06-17 | Anti-sulphation pasting mats for lead-acid batteries |
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| EP (1) | EP3158598B1 (en) |
| JP (1) | JP6814045B2 (en) |
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| WO (1) | WO2015195743A1 (en) |
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- 2015-06-17 EP EP15734756.8A patent/EP3158598B1/en active Active
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| WO2015195743A1 (en) | 2015-12-23 |
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| BR112016029242B1 (en) | 2022-08-09 |
| JP2017526107A (en) | 2017-09-07 |
| CA2952434A1 (en) | 2015-12-23 |
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| MX2016016729A (en) | 2017-08-18 |
| JP6814045B2 (en) | 2021-01-13 |
| PL3158598T3 (en) | 2021-08-16 |
| EP3158598B1 (en) | 2021-02-24 |
| US20170207435A1 (en) | 2017-07-20 |
| RU2686667C1 (en) | 2019-04-30 |
| BR112016029242A2 (en) | 2017-08-22 |
| CN106463681A (en) | 2017-02-22 |
| MY187574A (en) | 2021-09-30 |
| US11380962B2 (en) | 2022-07-05 |
| MX382816B (en) | 2025-03-13 |
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