CA2865474C - New pasting paper made of glass fiber nonwoven comprising carbon graphite - Google Patents
New pasting paper made of glass fiber nonwoven comprising carbon graphite Download PDFInfo
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- CA2865474C CA2865474C CA2865474A CA2865474A CA2865474C CA 2865474 C CA2865474 C CA 2865474C CA 2865474 A CA2865474 A CA 2865474A CA 2865474 A CA2865474 A CA 2865474A CA 2865474 C CA2865474 C CA 2865474C
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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
- 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
- H01M50/434—Ceramics
- H01M50/437—Glass
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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
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
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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
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
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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
- H01M50/411—Organic material
- H01M50/429—Natural polymers
- H01M50/4295—Natural cotton, cellulose or wood
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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
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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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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- Battery Electrode And Active Subsutance (AREA)
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Abstract
Description
NEW PASTING PAPER MADE OF GLASS FIBER NONWOVEN COMPRISING CARBON
GRAPHITE
[0001] Continue to [0002].
BACKGROUND OF THE INVENTION
Stated differently, the battery is in a partially charged state known as a PSOC (i.e., partial state of charge). Accordingly, a lead-acid battery used in an ISS vehicle is required to have a capability in which the battery is charged as much as possible in a relatively short time. In other words, the lead-acid battery should have a higher charge acceptance.
Therefore, improvements in the charge acceptance of a lead-acid battery are desired.
For example, during discharge of the lead-acid battery, the lead dioxide (a fairly good conductor) in the positive plate is converted to lead sulfate (an insulator). The lead sulfate can form an impervious layer encapsulating the lead dioxide particles which limits the utilization of lead dioxide often to less than 50 percent of capacity, and more commonly around 30 percent.
The low percentage of usage is a key reason why the power and energy performance of a lead-acid battery is inherently less than optimum. It is believed that this insulator layer leads to higher internal resistance for the battery. Improving the charge acceptance may also help reduce issues associated with formation of lead sulfate. In addition, lead-acid batteries having a separator typically exhibit a voltage drop when operated in cranking cycles at low operating temperatures (multiple starting procedures). This disadvantage hinders the acceptance of such battery systems for a broader use.
BRIEF SUMMARY OF THE INVENTION
The nonwoven fiber separator may include a mixture of glass fibers that may include a plurality of first glass fibers having diameters between about 8 pm to 13 pm and a plurality of second glass fibers having diameters of at least 6 pm. The plurality of second glass fibers may further include a silane material sizing. The nonwoven fiber separator may also include an acid resistant binder that bonds the plurality of first and second glass fibers to form the nonwoven fiber separator. The nonwoven fiber separator may further include a wetting component applied to the nonwoven fiber separator to increase the wettability of the nonwoven fiber separator such that the nonwoven fiber separator has or exhibits an average water wick height of at least 1.0 cm after exposure to water for 10 minutes conducted according to method IS08787. The nonwoven fiber separator may also include a conductive material disposed on at least one surface of the nonwoven fiber separator such that when the nonwoven fiber separator is positioned adjacent the positive or negative electrode, the conductive material contacts the positive or the negative electrode. The nonwoven fiber separator may have an electrical resistance of less than about 100,000 ohms per square to enable electron flow about the nonwoven fiber separator.
In another embodiment, a nonwoven fiber separator for an AGM battery, the nonwoven fiber separator is provided. The nonwoven fiber separator may include a mixture of glass fibers including a plurality of first glass fibers having diameters between about 8 pm to 13 pm and a plurality of second glass fibers having diameters of at least 6 pm. The plurality of second glass fibers may further include a silane material sizing.
The nonwoven fiber separator may also include an acid resistant binder that bonds the plurality of first and second glass fibers to form the nonwoven fiber separator. A wetting component may be applied to the nonwoven fiber separator to increase the wettability of the nonwoven fiber separator such that the nonwoven fiber separator has or exhibits an average water wick height of at least 1.0 cm after exposure to water for 10 minutes conducted according to method IS08787. The nonwoven fiber separator may further include a conductive material disposed on at least one surface of the nonwoven fiber separator such that when the nonwoven fiber separator is positioned adjacent a positive or a negative electrode of a lead-acid battery, the conductive material contacts the positive or negative electrode. The nonwoven fiber separator may have an electrical resistance of less than about 100,000 ohms per square to enable electron flow about the nonwoven fiber separator.
In another embodiment, a method of manufacturing a nonwoven fiber separator for use in a lead-acid battery is provided. The method may include providing a mixture of glass fibers including a plurality of first glass fibers having diameters between about 8 pm to 13 pm and a plurality of second glass fibers having diameters of at least 6 pm.
The plurality of second glass fibers may also include a silane material sizing. The method may also include applying an acid resistant binder to the mixture of glass fibers to couple the mixture of glass fibers together to form the nonwoven fiber separator. The method may further include applying a conductive material to at least one surface of the nonwoven fiber separator such that when the nonwoven fiber separator is positioned adjacent a positive or a negative electrode of a battery, the conductive material contacts the positive or the negative electrode. The nonwoven fiber separator may have an electrical resistance of less than about 100,000 ohms per square so as to enable electron flow about the nonwoven fiber separator. The method may additionally include applying a wetting component to the nonwoven fiber separator to increase the wettability of the nonwoven fiber separator such that the nonwoven fiber separator has or exhibits an average water wick height of at least 1.0 cm after exposure to water for 10 minutes conducted according to method IS08787.
BRIEF DESCRIPTION OF THE DRAWINGS
DETAILED DESCRIPTION OF THE INVENTION
For example, processes, and other elements in the invention may be shown as components in block diagram form in order not to obscure the embodiments in unnecessary detail. In other instances, well-known processes, structures, and techniques may be shown without unnecessary detail in order to avoid obscuring the embodiments.
Furthermore, not all operations in any particularly described process may occur in all embodiments. A process may correspond to a method, a function, a procedure, a subroutine, a subprogram, etc. When a process corresponds to a function, its termination corresponds to a return of the function to the calling function or the main function.
For example, during discharge of the lead acid battery, lead dioxide (a good conductor) in the positive electrode plate is converted to lead sulfate, which is generally an insulator.
The lead sulfate can form an impervious layer or layers encapsulating the lead dioxide particles, which may limit the utilization of the lead dioxide, and thus the battery, to less than 50 percent of capacity, and in some cases about 30 percent. The insulative lead sulfate layer may also lead to higher resistance for the battery. The effect may be a decrease in the electrical current provided by the battery and/or in the discharge life of the battery.
In some embodiments, the mat may offer a significant improvement (decrease) of the voltage drop when operated in cranking cycles at low operating temperatures (multiple starting procedures) if compared to existing systems. Conductive reinforcement mats may replace other plate reinforcement means, such as paper, that are currently used in lead-acid or other batteries. The conductive reinforcement mat provides several advantages over the current plate reinforcement means, such as not dissolving in the electrolyte (e.g., sulfuric acid);
providing vibration resistance, reducing plate shedding, strengthening or reinforcing the plate; and/or providing good dimensional stability, which may allow easier guiding or handling during battery plate manufacturing processes.
The route provided by the mat is typically separate from the route provided by the conductor plate or grid of the battery. The multiple electron paths (e.g., the mat and conductor plate) allows the electrons to flow via either or both the conductive reinforcement mat or the conductor plate/grid depending on which route provides the least electrical resistance. In this manner, as the electrode degrades due to formation of lead sulfate, numerous routes for the electrons are maintained, thereby extending the overall life of the battery.
In some embodiments, the battery may include a battery separator that also includes a conductive material. The battery separator may provide extra electron flow routes in addition to the fiber mat and conductor plate or grid. Such a separator may be particularly useful in AGM
batteries discussed herein. In some embodiments, the separator may include a non-conductive separating layer.
The conductive layer mat may be disposed across substantially the entire surface of the conductive reinforcement mat so that the electrically conductive layer is substantially equal in size and shape to the conductive reinforcement mat. In this manner the electrically conductive layer provides a large conductive surface that contacts the electrode.
of an inch to about 11A inches, although fiber lengths are more commonly about 1/3 inch to 'A
inch or 1 inch.
In another embodiment, the conductive material may be mixed with the binder and applied on the fiber mat during the binder application. The latter process represents a "one-step" or single application process. The binder may help bond the conductive material to the mat.
Having described several embodiments of the invention, additional aspects will be more apparent with reference to the figures described below.
The term "wettability" as used herein refers to the mats ability to wick or otherwise transport water and/or other solutions, such as a water and acid solution, from a location. For example, in testing the wettability or wickability of glass fiber mats, a strip of the mat, which is often about 1 inch in width, 6 inches long, and typically 0.1-3 mm thick, may be dipped vertically in water or another solution for a given amount of time, such as 10 minutes. The distance or height the water absorbs within the glass fiber mat from a surface of the water or other solution indicates the mat's ability to wick or otherwise transport the water or solution.
The test to determine the average water wick height of the reinforcement mat may be conducted according to method IS08787. In some embodiments, the wicking capability may also improve the wetting of the electrode with electrolyte.
In some embodiments, the wettable component may include starch, cellulose, stabilized cotton, a hydrophilic binder (e.g., a poly acrylic acid based binder) and the like. In some embodiments, the binder may protect the wettable component, such as cotton, from deterioration. In some embodiments, the glass mat may include only coarse glass fibers, or fibers having a fiber diameter of between about 6 and 30 pm. The wettable component may increase such mat's ability to absorb the water and/or water/acid solution and/or allow the water and/or water/acid solution to flow essentially along a surface of the reinforcement mat.
The component fibers and microfibers may function synergistically to wick water and/or the water/acid solution, and thus, may greatly improve the wettability/wickability of the reinforcement mat. For example, glass microfibers are typically more wettable than coarse glass fibers. The microfibers, however, may be covered or concealed by the coarse glass fibers and/or binder and, thus, not exposed to the water and/or water/acid solution.
In yet other embodiments, the average water wick height and or water/acid solution wick height may be greater than 1 cm after exposure to the respective solution for 10 min. As briefly described above, the addition of silane sized glass microfibers to the reinforcement mat may significantly increase the wettability/wickability of the reinforcement mat such that the average water wick height and/or water/acid solution wick height increases.
EMBODIMENTS
Separator 220 may also include one or more fiber mats that are positioned adjacent one or both sides of the microporous membrane/polymeric film to reinforce the microporous membrane and/or provide puncture resistance.
As shown in FIGS. 3A-3C, a reinforcement mat 230 may be disposed on both surfaces of the negative electrode 212, or may fully envelope or surround the electrode.
Likewise, although reinforcement mat 230 is shown on the outer surface of the electrode 212, in some embodiments reinforcement mat 230 may be positioned on the inner surface of the electrode 212 (i.e., adjacent separator 220). Reinforcement mat 230 reinforces the negative electrode 212 and provides an additional supporting component for the negative active material 214.
The additional support provided by reinforcement mat 230 may help reduce the negative effects of shedding of the negative active material particles as the active material layer softens from repeated charge and discharge cycles. This may reduce the degradation commonly experienced by repeated usage of lead-acid batteries.
For example, reinforcement mat 230 may be fully impregnated with the negative active material 214 so that reinforcement mat 230 is fully buried within the negative active material 214 (i.e., fully buried within the lead paste). Fully burying the reinforcement mat 230 within the negative active material 214 means that the mat is entirely disposed within the negative active material 214.
In one embodiment, reinforcement mat 230 may be disposed within the negative active material 214 up to about a depth X of about 20 mils (i.e., 0.020 inches) from an outer surface of the electrode 212. In other embodiments, the glass mat 230 may rest atop the negative active material 214 so that the mat is impregnated with very little active material. Often the reinforcement mat 230 will be impregnated with the negative active material 214 so that the outer surface of the mat forms or is substantially adjacent the outer surface of the electrode 212 (see reinforcement mat 240). In other words, the active material may fully penetrate through the reinforcement mat 230 so that the outer surface of the electrode 212 is a blend or mesh of active material and reinforcement mat fibers.
The conductive material may then be dispersed in a secondary or dilute binder that is then coated or sprayed onto the surface of reinforcement mat 230. Reinforcement mat 230 may then be cured so that the conductive material forms a conductive layer across the entire surface, or a defined portion, of reinforcement mat 230. In this embodiment, a majority of the conductive material may be positioned atop the surface of reinforcement mat 230.
In another embodiment, the component fibers may be mixed with the glass fibers such that upon forming the glass mat the component fibers are entangled with and bonded to the glass fibers. In yet other embodiments, the wetting component may be a combination of the above described wetting components (i.e., a binder having a wettable component, a wettable solution, and/or a component fiber).
Reinforcement mat 302 may also include a wetting component as described above to provide the mat 302 with enhanced wettability characteristics. Reinforcement mat 302 may partially or fully cover the outer surface of electrode 300. The configuration of FIG. 3B is similar to that of FIG. 3A except that an additional reinforcement mat 304 is disposed on or near an opposite surface of electrode 300 so that electrode 300 is sandwiched between the two glass mats, 302 and 304. Either or both reinforcement mats, 302 and 304, may include a conductive material and/or layer to enable electron flow to a battery terminal as well as a wetting component. As such, electrode 300 may be sandwiched between two conductive reinforcement mats 302 and 304. FIG. 3C illustrates a configuration where a reinforcement mat 306 envelopes or surrounds electrode 300. Although FIG. 3C illustrates the reinforcement mat 306 fully enveloping the electrode 300, in many embodiments a top side or portion of the mat 306, or a portion thereof, is open. Glass mat 306 may include the conductive material and/or layer as described above to enable electron flow as well as a wetting component.
Reducing the volume of reinforcement mat 230 helps minimize the battery's volume of non-electrochemically contributing components.
As described above, the binder is generally an acid and/or chemically-resistant binder that delivers the durability to survive in the acid environment throughout the life of the battery, the strength to survive the plate pasting operation, and the permeability to enable paste penetration. For example, the binder may be an acrylic binder, a melamine binder, a UF
binder, or the like. The binder may also include and bond the conductive material to the first and/or second coarse fibers. Increased binder usage may reduce the thickness of reinforcement mat 230 by creating more fiber bonds and densifying reinforcement mat 230.
The increased fibers bonds may also strengthen reinforcement mat 230. In one embodiment, the binder is applied to the first and second coarse fibers such that the binder comprises between about 5% and 45% by weight of the reinforcement mat 230 or between about 15% and 35% by weight of the reinforcement mat. In another embodiment, the binder is applied to the first and second coarse fibers such that it comprises between about 5% and 30% by weight of the reinforcement mat 230.
The resulting reinforcement mat 230 may have or exhibit an average water wick height of at least 0.5 cm after exposure to water for 10 minutes conducted according to method IS08787. The wetting component is dissolvable in an acid solution of the lead-acid battery such that a significant portion of the nonwoven fiber mat is lost due to dissolving of the wetting component. For example, between about 5-85% of the mass of the reinforcement mat 230 may be lost.
Specifically, the reinforcement mat 230 has a tensile strength in the machine direction of at least 22 lbs/3 inch and a tensile strength in the cross-machine direction of at least 13 lbs/3 inch. The above described mats have been found to have sufficient strength to support the active material and to withstand the various stresses imposed during plate or electrode manufacturing and processing (e.g., pasting or applying the active material).
Reinforcement mat 230 that do not have the above described tensile strength attributes may not be sufficiently strong to support the applied active material (e.g., prevent shedding and the like) and/or may pose processing issues, such as mat breakage when applying the active material (e.g., lead or lead oxide) paste on the glass mat during the plate reinforcement process.
For example, electrons proximate to grid/conductor 216 may flow along grid/conductor 216 and/or reinforcement mat 230 to terminal 218 while electrons proximate to separator 220 flow along an electrical path of separator 220 to terminal 218. Similarly, electrons proximate to grid/conductor 206 may flow along grid/conductor 206 and/or reinforcement mat 240 to terminal 208 while electrons proximate to separator 220 flow along an electrical path of separator 220 to terminal 208. In such embodiments, the available or possible electron paths may be greatly increased. In embodiments where the separator includes conductive materials, there is a nonconductive layer and/or other nonwoven nonconductive mat positioned against the conductive portion of the separator. In embodiments not utilizing another nonwoven nonconductive mat, the conductive material in the separator may be positioned on or near a surface of the separator such that at least one nonconductive layer extends through a center of the separator.
The process may involve transporting a lead alloy grid 410 on a conveyor toward an active material 430 applicator (e.g., lead or lead oxide paste applicator), which applies or pastes the active material 430 to the grid 410. A nonwoven mat roll 420 may be positioned below grid 410 so that a reinforcement mat is applied to a bottom surface of the grid 410. The reinforcement mat may include a conductive material and/or layer, as well as a wetting component, as described herein. In some embodiments, the reinforcement mat may also include a blend of coarse fibers as described herein. In some embodiments, the reinforcement mat may also include a blend of coarse and micro glass fibers in addition to the wetting component as described herein. A second nonwoven mat roll 440 may be positioned above grid 410 so that a second reinforcement mat is applied to a top surface of the grid 410. The second reinforcement mat may also include a conductive material, a wetting component, and/or layer and/or blend of coarse fibers and/or microfibers (similar to or different from reinforcement mat 420). The resulting electrode or plate 450 may subsequently be cut to length via a plate cutter (not shown). As described herein, the active material 430 may be applied to the grid 410 and/or top and bottom of reinforcement mats, 440 and 420, so that the active material impregnates or saturates the mats to a desired degree. The electrode or plate 450 may then be dried via a dryer (not shown) or other component of process 400. As described herein, the reinforcement mats, 440 and 420, may aid in the drying of the electrode or plate 450 by wicking the water and/or water/acid solution from the electrode or plate 450 so as to allow the water and/or water/acid solution to evaporate.
The grid of lead alloy material may be either for a positive electrode (e.g., grid/conductor 206) or a negative electrode (e.g., grid/conductor 216) of a battery. At block 520, a paste of active material is applied to the grid of lead alloy material to form a battery plate or electrode (i.e., negative or positive electrode). At block 530, a nonwoven fiber mat is applied to a surface of the paste of the active material such that the nonwoven fiber mat is disposed at least partially within the paste of active material. As described herein, the nonwoven fiber mat may include a plurality of fibers, a binder material that couples the plurality of fibers together, a wetting component, and a conductive material disposed at least partially within the nonwoven fiber mat so as to contact the paste of active material. The wetting component may provide a wicking capability to allow a complete wetting of the electrodes of a lead-acid battery. The conductive material may be any material described herein and/or a conductive layer that is formed on the nonwoven fiber mat. The nonwoven fiber mat may have an electrical resistant of less than about 100,000 ohms per square to enable electron flow on a surface of the nonwoven fiber mat. In some embodiments, the nonwoven fiber mat may be disposed within the paste of active material between about 0.001 inches and about 0.020 inches.
The binder may be applied to the mat between about 5% and 45% by weight, between about 20% and 30% by weight, and the like. In some embodiments, the conductive material may include a plurality of conductive fibers that are entangled with fibers of the nonwoven fiber mat.
At block 610, a plurality of glass fibers are provided. The glass fibers may be coarse fibers, microfibers, or a combination of coarse and microfibers. At block 620, an acid resistant binder is applied to the plurality of glass fibers to couple the plurality of glass fibers together to form the reinforcement mat. At block 630, a wetting component is added to the glass fibers and/or reinforcement mat to increase the wettability/wickability of the reinforcement mat. As described herein, the wettability/wickability of the reinforcement mat may be increased such that the reinforcement mat has or exhibits an average water wick height and/or average water/acid solution wick height of at least 0.5 cm after exposure to the respective solution for 10 minutes in accordance with the test conducted according to method IS08787. A conductive material may be applied to the glass fibers and/or reinforcement mat at block 640. Applying the conductive material may include providing a layer of conductive fibers and/or other conductive materials and positioning this layer atop the glass mat. The conductive material may also include a coating that is applied to the mat.
In some embodiments, the conductive material may be added to a binder that is applied to the fiber mat. In other embodiments, the conductive material may include conductive fibers that are disposed at least partially within and/or entangled with the fiber mat.
from Dow Chemical). The suspension mixture was prepared such that it contained approximately 0.5% binder and 1.5% graphene. A spray gun was then used to apply the mixture to a glass mat (Dura-Glass mat PR-9 and B-10). The mat was then dried at 125C
for approximately 1 hr and cured at 175C for approximately 3 mins. The surface resistance was then measured and the results are provided in Table 1 below.
Surface Weight Surface Sample Sample resistivity before resistance length width (K- coating Sample (K-Ohm) (cm) (cm) Ohm/sq.) (g) Graphene%
B-10 (1) 1.84 14.3 12.2 1.6 0.7609 15.8%
B-10 (2) 3.41 14.2 12.2 2.9 0.7643 14.5%
B-10 (3) 2.25 14.2 11.9 1.9 0.7334 17.3%
PR-9 (1) 13.76 14.2 12 11.6 0.4577 10.1%
PR-9 (2) 18.26 14.2 12.3 15.8 0.4651 11.7%
PR-9 (3) 5.29 14.7 12.2 4.4 0.4728 ; 8.9%
Table 1: Reinforcement Mat Using Graphene as a Conductive Coating
As such, the graphene coated glass mats experience similar weight loss as uncoated glass mats. However, a slight drop in conductivity was observed after the mat was exposed to sulfuric acid for an extended time. This slight drop in conductivity may indicate reaction between the graphene and sulfuric acid.
HA-16 from Dow Chemical). The suspension mixture was prepared such that it contained approximately 1% binder (or no binder) and 0.5% CNS. A glass mat (Dura-Glass mat PR-9 or uncoated polyester spunbond mat) was placed in the mixture and water was vacuumed out. A uniform coating of the CNS was obtained. The mat was then dried at 125C
for approximately 1 hr and cured at 175C for approximately 3 mins. The surface resistance was then measured and the results are provided in Table 2 below.
Surface Sample Sample Surface resistance length width resistivity Sample (Ohm) (inch) (inch) (Ohm/sq.) CNS ctio Comment PR-9 (1) 180 14 12 154.3 2.50% With binder Without PR-9 (2) 65 14 14 65.0 15% binder PR-9 (3) 53 14 14 53.0 25% With binder Without PR-9 (4) 50 14 14 50.0 15% binder Without PR-9 (5) 66 14 14 66.0 25% binder Polyester (1) 239 13.5 13.5 239.0 0.3% With binder Polyester (2) 68 13.5 13.5 68.0 2% With binder Polyester (2) 132 13.5 13.5 132.0 0.66% With binder Table 2: Reinforcement Mat Using CNS (Carbon Nanostructure) as a Conductive Coating
Given these results, CNS may be a better choice as a conductive coating than graphene.
Further, the CNS coating provides a much better conductivity (i.e., less resistance) than graphene on non-woven mats. For example, as shown in Table 1, K-ohm units are used for graphene resistance, whereas in Table 2, Ohm units are used for CNS
resistance.
The wettability/wickability tests were conducted according to method IS08787.
The mats were exposed to both a water solution and a water/acid solution where the concentration of sulfuric acid was approximately 40%. The results of the tests are shown in Table 3 below.
Average Average acid water wicking wicking (40%) height height after after Sample Sample 10mins 10mins ID description Binder (cm) Std Dev (cm) Std Dev 100%
coarse RHOPLEXTM
Control glass fibers HA-16 0.0 0 0.0 0.0 50% 3/4"
K249 T, 50% RHOPLEXTM
1 cellulose HA-16 0.8 0.15 1.2 0.12 50% 3/4"
K249 T, 50% Hycar FF
2 cellulose 26903 0.9 0.15 0.9 0.15 50% 3/4"
K249 T, 25%
cellulose, 25% 206-253 Hycar FF
3 26903 2.7 0.05 1.9 0.25 Table 3: Sample Reinforcement Mat
coarse glass fibers (T glass fibers) having an average fiber length of approximately 34 " and an average fiber diameter of approximately 13 pm. The glass fibers were bonded together with an acid resistant binder sold by Dow Chemical under the trade name RHOPLEXTM HA-16.
The acid resistant binder was applied so as to have a Loss on Ignition (L01) of approximately 20%.
The control mat exhibited an average water wicking height and an average acid wicking height of approximately 0.0 cm after exposure to the respective solutions for 10 minutes.
Stated differently, the control mat exhibited essentially no wettability/wickability.
coarse glass fibers having an average fiber length of approximately 1/4" and an average fiber diameter of approximately 13 pm and to include 50% cellulose fibers having an average fiber length of approximately 2.40 mm. The cellulose fibers were made from a pulp slurry by pre-soaking a Kraft board in water (e.g., Kamloops Chinook Kraft board manufacture by Domtar) and stirring the soaked Kraft board in water for at least 10 minutes. The cellulose fiber pulp slurry was then combined with the glass fibers. The coarse glass fibers and cellulose fibers were bond together with the RHOPLEXTM HA-16 binder so as to have an LOI of approximately 20%. The first mat exhibited an average water wicking height of approximately 0.8 cm with a standard deviation of 0.15 after exposure to the water solution for 10 minutes. The first mat also exhibited an average water/acid solution wicking height of approximately 1.2 cm with a standard deviation of 0.12 after exposure to the water/acid solution for 10 min.
coarse glass fibers and 50% cellulose fibers having fiber properties similar to the first mat.
The coarse glass fibers and cellulose fibers were bond together with an acid resistant binder sold by Lubrizol under the trade name Hycar FF 26903. The binder was applied so as to have an LOI of approximately 20%. The second mat exhibited an average water wicking height of approximately 0.9 cm with a standard deviation of 0.15 after exposure to the water solution for 10 minutes. The second mat also exhibited an average water/acid solution wicking height of approximately 0.9 cm with a standard deviation of 0.15 after exposure to the water/acid solution for 10 min.
coarse glass fibers and 25% cellulose fibers having fiber properties similar to the first and second mats. The third mat also included approximately 25% glass microfibers having an average fiber diameter of approximately 0.76 pm (i.e., Johns Manville 206-253 fibers). The coarse glass fibers, glass microfibers, and cellulose fibers were bond together with the Hycar FF 26903 binder so as to have an LOI of approximately 20%. The third mat exhibited an average water wicking height of approximately 2.7 cm with a standard deviation of 0.05 after exposure to the water solution for 10 minutes. The third mat also exhibited an average water/acid solution wicking height of approximately 1.9 cm with a standard deviation of 0.25 after exposure to the water/acid solution for 10 min.
include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a process" includes a plurality of such processes and reference to "the device"
includes reference to one or more devices and equivalents thereof known to those skilled in the art, and so forth.
Claims (20)
a positive electrode;
a negative electrode;
a nonwoven fiber mat separator positioned between the positive electrode and the negative electrode, the nonwoven fiber separator comprising:
a mixture of glass fibers comprising:
a plurality of first glass fibers having diameters between about 8 µm to 13 µm; and a plurality of second glass fibers having diameters of at least 6 µm, the plurality of second glass fibers comprising a silane material sizing;
an acid resistant binder that bonds the plurality of first and second glass fibers to form the nonwoven fiber separator;
a wetting component applied to the nonwoven fiber separator to increase the wettability of the nonwoven fiber separator such that the nonwoven fiber separator has or exhibits an average water wick height of at least 1.0 cm after exposure to water for 10 minutes conducted according to method IS08787; and a conductive material disposed on at least one surface of the nonwoven fiber separator such that when the nonwoven fiber separator is positioned adjacent the positive or negative electrode, the conductive material contacts the positive or the negative electrode, the nonwoven fiber separator having an electrical resistance of less than about 100,000 ohms per square to enable electron flow about the nonwoven fiber separator.
a mixture of glass fibers comprising:
a plurality of first glass fibers having diameters between about 8 pm to 13 µm; and a plurality of second glass fibers having diameters of at least 6 µm, the plurality of second glass fibers comprising a silane material sizing;
an acid resistant binder that bonds the plurality of first and second glass fibers to form the nonwoven fiber separator;
a wetting component applied to the nonwoven fiber separator to increase the wettability of the nonwoven fiber separator such that the nonwoven fiber separator has or exhibits an average water wick height of at least 1.0 cm after exposure to water for 10 minutes conducted according to method IS08787; and a conductive material disposed on at least one surface of the nonwoven fiber separator at such that when the nonwoven fiber separator is positioned adjacent a positive or a negative electrode of a lead-acid battery, the conductive material contacts the positive or negative electrode, the nonwoven fiber separator having an electrical resistance of less than about 100,000 ohms per square to enable electron flow about the nonwoven fiber separator.
providing a mixture of glass fibers comprising:
a plurality of first glass fibers having diameters between about 8 µm to 13 µm; and a plurality of second glass fibers having diameters of at least 6 µm, the plurality of second glass fibers comprising a silane material sizing;
applying an acid resistant binder to the mixture of glass fibers to couple the mixture of glass fibers together to form the nonwoven fiber separator;
applying a conductive material to at least one surface of the nonwoven fiber separator such that when the nonwoven fiber separator is positioned adjacent a positive or a negative electrode of a battery, the conductive material contacts the positive or the negative electrode, the nonwoven fiber separator having an electrical resistance of less than about 100,000 ohms per square so as to enable electron flow about the nonwoven fiber separator; and applying a wetting component to the nonwoven fiber separator to increase the wettability of the nonwoven fiber separator such that the nonwoven fiber separator has or exhibits an average water wick height of at least 1.0 cm after exposure to water for 10 minutes conducted according to method 1S08787.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US14/045,579 US9923196B2 (en) | 2013-10-03 | 2013-10-03 | Conductive mat for battery electrode plate reinforcement and methods of use therefor |
| US14/045,579 | 2013-10-03 | ||
| US14/048,771 US10062887B2 (en) | 2013-10-08 | 2013-10-08 | Battery electrode plate reinforcement mat having improved wettability characteristics and methods of use therefor |
| US14/048,771 | 2013-10-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2865474A1 CA2865474A1 (en) | 2015-04-03 |
| CA2865474C true CA2865474C (en) | 2021-11-16 |
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| CA2865474A Active CA2865474C (en) | 2013-10-03 | 2014-10-02 | New pasting paper made of glass fiber nonwoven comprising carbon graphite |
| CA2865475A Active CA2865475C (en) | 2013-10-03 | 2014-10-02 | New pasting paper made of glass fiber nonwoven comprising carbon graphite |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2865475A Active CA2865475C (en) | 2013-10-03 | 2014-10-02 | New pasting paper made of glass fiber nonwoven comprising carbon graphite |
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| EP (2) | EP2858142B1 (en) |
| CA (2) | CA2865474C (en) |
| ES (2) | ES2645137T3 (en) |
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| SI (1) | SI2858143T1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160372727A1 (en) * | 2015-06-17 | 2016-12-22 | Johns Manville | Bi-functional nonwoven mat used in agm lead-acid batteries |
| US20170346076A1 (en) * | 2016-05-31 | 2017-11-30 | Johns Manville | Lead-acid battery systems and methods |
| WO2018147866A1 (en) * | 2017-02-10 | 2018-08-16 | Daramic, Llc | Improved separators with fibrous mat, lead acid batteries, and methods and systems associated therewith |
| US10622639B2 (en) | 2017-02-22 | 2020-04-14 | Johns Manville | Acid battery pasting carrier |
| KR20240108534A (en) * | 2017-09-08 | 2024-07-09 | 다라믹 엘엘씨 | Improved lead acid battery separators incorporating carbon |
| US20190181506A1 (en) * | 2017-12-12 | 2019-06-13 | Hollingsworth & Vose Company | Pasting paper for batteries comprising multiple fiber types |
| CN110261294B (en) * | 2019-06-04 | 2022-04-19 | 中国船舶重工集团公司第七二五研究所 | Electrochemical test device for simulating metal corrosion of crack area under deep sea environment |
| CN113213493B (en) * | 2021-04-13 | 2023-05-26 | 武汉纽赛儿科技股份有限公司 | Granati-shaped silicon oxide-nitrogen doped carbon composite material, synthesis method thereof and lithium ion capacitor |
| WO2025128119A1 (en) * | 2023-12-15 | 2025-06-19 | Owens Corning Intellectual Capital, Llc | Rotary-formed glass fibers |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB824025A (en) * | 1957-03-25 | 1959-11-25 | Chloride Electrical Storage Co | Improved separators for lead acid electric accumulators |
| JPH03203158A (en) * | 1989-12-28 | 1991-09-04 | Shin Kobe Electric Mach Co Ltd | Lead-acid battery |
| JP2797634B2 (en) * | 1990-04-26 | 1998-09-17 | 日本板硝子株式会社 | Storage battery separator |
| US5250372A (en) | 1991-08-21 | 1993-10-05 | General Motors Corporation | Separator for mat-immobilized-electrolyte battery |
| SI2464773T1 (en) * | 2009-08-11 | 2017-12-29 | Johns Manville | Process for binding fiberglass and fiberglass product |
| US9118065B2 (en) | 2010-05-27 | 2015-08-25 | Johns Manville | Lead-oxide battery plate with nonwoven glass mat |
| JP6088500B2 (en) | 2011-06-23 | 2017-03-01 | モレキュラー レバー デザイン,エルエルシー | Lead acid battery formulation containing discrete carbon nanotubes |
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2014
- 2014-10-01 ES ES14187303.4T patent/ES2645137T3/en active Active
- 2014-10-01 ES ES14187304.2T patent/ES2622752T3/en active Active
- 2014-10-01 EP EP14187303.4A patent/EP2858142B1/en active Active
- 2014-10-01 EP EP14187304.2A patent/EP2858143B1/en active Active
- 2014-10-01 SI SI201430194A patent/SI2858143T1/en unknown
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Also Published As
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| EP2858143B1 (en) | 2017-02-01 |
| EP2858143A1 (en) | 2015-04-08 |
| PL2858142T3 (en) | 2018-02-28 |
| CA2865475A1 (en) | 2015-04-03 |
| ES2645137T3 (en) | 2017-12-04 |
| CA2865475C (en) | 2021-11-30 |
| EP2858142A1 (en) | 2015-04-08 |
| ES2622752T3 (en) | 2017-07-07 |
| CA2865474A1 (en) | 2015-04-03 |
| SI2858143T1 (en) | 2017-06-30 |
| PL2858143T3 (en) | 2017-07-31 |
| EP2858142B1 (en) | 2017-09-20 |
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