New pasting paper made of glass fiber nonwoven comprising carbon graphite

[0001] Various materials for lead batteries have been disclosed in the prior art. For example, Japanese Patent Document JP H03 203158 A discloses a lead-acid battery containing a separator to which a glass mat is attached, and International Patent Application Publication No. WO 2011/019597 A1 relates to a fiberglass mat consolidated with a curable composition containing reducing sugars, which are suitable as a battery separator. Additionally, British Patent Document GB 824 025 A discloses a ribbed separator consisting mainly of cotton linters for lead-acid batteries, and Japanese Patent Document JP H04 10353 A relates to a mixture of glass fibers as a layer serving as the main body of the separator.

[0002] Lead-acid batteries are characterized as inexpensive and highly reliable. As such, they are widely used as an electrical power source for starting motor vehicles, golf carts and other electric vehicles. In recent years, various measures have been considered to reduce fuel consumption to prevent atmospheric pollution and global warming. Examples of motor vehicles subject to measures to improve fuel economy that are considered include vehicles with start / stop systems (ISS vehicles) where the engine is turned off when the vehicle is stationary to prevent unnecessary idle engine operation and reduce engine running time.

[0003] In an ISS vehicle, the number of engine starts is higher and the lead-acid battery discharges the high current during each start. In addition, the amount of electricity generated by the alternator on the ISS is smaller and the lead-acid battery is intermittently charged. As such, charging the battery is often insufficient. In other words, the battery is in a partially charged state, known as PSOC (this is a partially charged state partial state of charge). Thus, it is required that the lead-acid battery used in the ISS vehicle should be able to charge as much as possible in a relatively short time. In other words, a lead-acid battery should have a higher capacity to accept charge. Therefore, improvements to the charge acceptance of the lead-acid battery are desirable.

[0004] Lead-acid batteries usually have a shorter useful life when operated in PSOC mode than when the battery is operated in a fully charged state. It is believed that one of the reasons for the shorter service life in the PSOC state is repeated charging and recharging the battery in an insufficiently charged state. Charging and recharging the battery in this way negatively affects the electrodes or the battery plates. For example, during discharging, lead sulphate forms on the negative plate and undergoes gradual expansion during charging, with no tendency to return to metallic lead. Improving charge intake can prevent the battery from charging and recharging in an insufficiently charged state, which may inhibit sulfate growth

Lead caused by repeated charging / discharging. This can extend the life of the lead-acid battery.

[0005] In addition, there are inherent disadvantages of lead-acid batteries. For example, when discharging a lead battery, lead dioxide (a fairly good conductor) on the positive plate is converted into lead sulfate (insulator). Lead sulfate can form an impermeable layer surrounding the lead dioxide particles, which limits the use of lead dioxide often to less than 50 percent of the yield, and even more often about 30 percent. The low percentage of utilization is the main reason why the power and energy characteristics of a lead-acid battery are inherently less than optimal. It is believed that this insulation layer leads to higher internal battery resistance. Improving charge intake can also help reduce the problems associated with lead sulfate formation. In addition, lead-acid batteries having a separator usually show a voltage drop when operated in crankshaft rotation cycles at low operating temperatures (multiple start-up procedures). This disadvantage makes it difficult to accept such battery systems for wider use.

BRIEF SUMMARY OF THE INVENTION [0006] The embodiments described herein provide non-woven fiber mats that can be used to reinforce plates in lead-acid batteries and / or that have an electrically conductive surface that improves the flow of electrons from the battery plates. In addition to reinforcing the battery plates or electrodes, the nonwoven fiber mats described herein can improve the charge uptake of a lead-acid battery. The non-woven mats described here can also offer a significant improvement (reduction) in voltage drop when used in crankshaft rotation cycles at low operating temperatures (multiple start-up procedures) compared to existing systems. According to one embodiment, a lead-acid battery is provided as defined in claim 1. The lead-acid battery contains a positive electrode, a negative electrode, a separator placed between the positive electrode and a negative electrode for electrical isolation of the positive and negative electrode and a non-woven fiber mat (reinforcing mat), which is placed adjacent to the positive electrode or negative electrode to strengthen the electrode positive or negative. The battery may also contain a non-woven fiber mat that is used to reinforce the separator. The reinforcement may contain a relatively homogeneous mixture of thick glass fibers. The coarse glass fiber mixture may comprise a plurality of first glass fibers having a diameter between 8 μm and 13 μm and a plurality of second glass fibers having a diameter of at least 6 μm. In some embodiments, the diameter of the second glass fibers is in the range between 6 μm and 7 μm. Many second glass fibers have a silane coating or sizing. Silane sizing of glass fibers can improve the fiber's resistance to acid. In addition, silane glued improves the wick characteristics of the fibers compared to non-glued fibers. The glass fiber mixture comprises first glass fibers having a diameter between 8 and 13 μm and second glass fibers

EP 2 858 142 B1 having sized with silane material and a diameter of at least 6 μm. In a preferred embodiment, the first and second glass fibers have different diameters.

[0007] The non-woven fiber mat further comprises an acid-resistant binder that binds a plurality of first and second glass fibers to form a non-woven fiber mat. The non-woven fiber mat contains a wetting component applied to the non-woven fiber mat to increase the wettability of the non-woven fiber mat such that the non-woven fiber mat has or exhibits an average wick-up height of at least 1.0 cm when exposed to water for 10 minutes , determined in accordance with IS08787. The non-woven fiber mat further comprises a conductive material that is disposed on at least one surface of the non-woven fiber mat or in a non-woven fiber mat, such that when the non-woven fiber mat is placed adjacent to the positive or negative electrode, the conductive material contacts the electrode positive or negative. A non-woven fiber mat can have an electrical resistance of less than 100,000 ohms per square, so as to allow electrons to flow through the non-woven fiber mat.

[0008] In some embodiments, the thick glass fiber mixture may contain between 10% and 95% of the first glass fibers and between 5% and 80% of the second glass fibers. In some embodiments, the non-woven fiber mat can have a surface weight of between 10 g / m2² a 100 g / m2². In some embodiments, the wetting component may contain one or more of cotton fibers, cellulose fibers or polyester fibers that are bonded to a non-woven fiber mat. In some embodiments, one or more of cotton fibers, cellulose fibers or polyester fibers may form a mat that is bonded to at least one side of the non-woven fiber mat. In some embodiments, one or more of cotton fibers, cellulose fibers or polyester fibers may be entangled in a mixture of thick glass fibers to form a non-woven fiber mat.

[0009] In some embodiments, the binder may comprise a plurality of conductive fibers and / or conductive particles. For example, the conductive material may contain graphite powder and / or a plurality of carbon fibers that are entangled in a mixture of thick glass fibers of a non-woven fiber mat.

[0010] According to another embodiment, a non-woven fiber mat for lead-acid battery is provided. The non-woven fiber mat may contain a relatively homogeneous mixture of thick glass fibers. The glass fiber mixture contains a plurality of first glass fibers having a diameter between 8 μm and 13 μm and a plurality of second glass fibers having a diameter of at least 6 μm, preferably 6 μm to 7 μm. Many second glass fibers contain sized silane material. The non-woven fiber mat also contains an acid-resistant binder material that binds many first and second glass fibers to form a non-woven fiber mat. The non-woven fiber mat contains a wetting component applied to the non-woven fiber mat to increase the wettability of the non-woven fiber mat such that the non-woven fiber mat has or exhibits an average wick-up height of at least 1.0 cm after exposure to water for 10 minutes , determined in accordance with ISO8787. The non-woven fiber mat further comprises a conductive material that is disposed on at least one surface

In a non-woven fiber mat or in a non-woven fiber mat, such that when the non-woven fiber mat is placed adjacent to the positive or negative electrode of the lead-acid battery, the conductive material contacts the positive or negative electrode. A non-woven fiber mat can have an electrical resistance of less than 100,000 ohms per square to allow electrons to flow on the surface of the non-woven fiber mat.

[0011] In some embodiments, the non-woven fiber mat can have a surface weight of between 20 g / m² a 60 g / m2². In some embodiments, the wetting component may include cotton fibers having diameters between 0.1 μm and 10 μm. In some embodiments, the non-woven fiber mat may contain between 70% and 95% of a thick glass fiber mixture and between 5% and 30% binder. In some embodiments, the thick glass fiber mixture may contain between 10% and 95% of the first glass fibers and between 5% and 80% of the second glass fibers. In some embodiments, the conductive material may further comprise carbon fibers that are between 8 mm to 12 lengths and have diameters between 6 μm and 10 μm. In some embodiments, the binder may contain one or more of acrylic, melamine, phenol and urea formaldehyde (UF) binder and / or any mixture thereof.

[0012] According to another embodiment, a method of making a non-woven fiber mat for use in a lead-acid battery is provided. The method includes providing a mixture of thick glass fibers. The thick glass fiber mixture contains a plurality of first glass fibers having a diameter between 8 μm and 13 μm and a plurality of second glass fibers having a diameter of 6 μm, preferably 6 μm to 7 μm. Many second glass fibers contain sized silane material. The method involves applying an acid-resistant binder to a thick glass fiber mixture to bond the thick glass fiber mixture together to form a non-woven fiber mat. The method also includes applying a conductive material to at least one surface of the non-woven fiber mat or in a non-woven fiber mat, such that when the non-woven fiber mat is placed adjacent to the positive or negative electrode of the battery, the conductive material contacts the positive or negative electrode. A non-woven fiber mat can have an electrical resistance of less than 100,000 ohms per square, so as to allow electrons to flow through the non-woven fiber mat. The method further includes applying a wetting component to the non-woven fiber mat to increase the wettability of the non-woven fiber mat such that the non-woven fiber mat has or exhibits an average wick pull-up height of at least 1.0 cm when exposed to water for 10 minutes as determined by the method in accordance with ISO8787.

[0013] In some embodiments, the use of a wetting component may include binding one or more of cotton fibers, cellulose fibers or polyester fibers to a mixture of thick glass fibers to form a non-woven fiber mat. In some embodiments, the conductive material comprises one or more of graphite particles or carbon fibers.

EP 2 858 142 B1

BRIEF DESCRIPTION OF THE DRAWINGS [0014] The invention is described in connection with the attached figures:

Fig. 1 is an exploded perspective view of the battery cell assembly.

Fig. 2 is a cross-sectional view of the assembled battery cell assembly of Fig. 1.

Figures 3A-3C show cross sections of different electrode or plate configurations and a non-woven fiber mat.

Fig. 4 shows a method for producing an electrode or plate having a non-woven fiber mat disposed on or near the surface of the electrode or plate.

Fig. 5 shows a method for manufacturing a lead-acid battery plate.

Fig. 6 shows a method for producing a non-woven fiber mat according to an embodiment of the invention.

[0015] In the attached figures, similar components and / or features may have the same numerical reference label. In addition, different components of the same type can be distinguished by tracking a reference label using a letter that distinguishes between similar components and / or features. If only the first numerical reference label is used in the specification, the description applies to any of the similar components and / or features having the same numerical reference label, irrespective of the letter suffix.

DETAILED DESCRIPTION OF THE INVENTION [0016] The following description provides specific details to provide a thorough understanding of the embodiment. However, it will be understood by those skilled in the art that embodiments can be implemented without these specific details. For example, the processes and other elements in the invention may be shown as components in a simplified diagram in order not to obscure the embodiment with unnecessary details. In other embodiments, well-known processes, constructions and techniques can be shown without unnecessary details to avoid obfuscating the embodiment.

[0017] It is also noted that individual embodiments can be described as a process that is represented as a flowchart, block flowchart, block flowchart, structural flowchart or simplified flowchart. Although a flowchart may describe operations as a sequential process, many operations can be performed in parallel or concurrently. In addition, the order of operations can be changed. The process can be terminated when its operations are completed, but may have additional stages not discussed or not included in the figure. In addition, not all operations in any, specifically described process, must occur in all forms of implementation. The process may correspond to a method, function, procedure, subroutine,

In a subprogram, etc. When a process corresponds to a function, its termination corresponds to the return of the function to the calling function or to the main function.

[0018] The invention provides non-woven fiber mats (hereinafter referred to as reinforcement mats) which have an electrically conductive surface to improve the flow of electrons to and / or from the battery plates, as well as contain a wetting component to improve the wettability of the mats. Reinforcing mats can be used to strengthen plates in lead-acid batteries or other accumulators, or used in separators placed between electrodes, e.g. in battery applications, absorption glass mat (AGM). The reinforcing mats can be any woven mat or preferably any non-woven mat that is acid resistant, such as a glass mat, or a mat made of mainly polyolefin fibers, or a mixture of polyolefin and glass fibers.

[0019] The flow of electrons is improved by providing a mat having a conducting surface or surfaces and / or other conducting path. Improved electron flow extends the service life of the battery, especially in lead-acid batteries, where continuous battery discharge and recharge results in a deterioration of the battery's electrodes. For example, when discharging a lead battery, the lead dioxide (good conductor) on the positive electrode plate is converted to lead sulfate, which is generally an insulator. Lead sulfate can form an impermeable layer or layers that surround lead dioxide particles, which can limit the use of lead dioxide and thus the battery, often to less than 50 percent in efficiency, and in some cases around 30 percent. An insulating layer of lead sulfate can also lead to higher battery resistance. The result can be a reduction in the electric current supplied by the battery and / or a reduction in the battery discharge time. In some embodiments, the mat can also offer a significant improvement (reduction) in voltage drop when used in crankshaft rotation cycles at low operating temperatures (multiple start-up procedures) compared to existing systems. Conductive reinforcing mats can replace other plate reinforcing agents, such as paper, that are currently used in lead-acid or other batteries. Conductive reinforcing mat provides a number of advantages over current plate reinforcing agents such as insolubility in electrolyte (e.g. sulfuric acid); providing vibration resistance, reducing panel loss, reinforcing or reinforcing the panel; and / or providing good dimensional stability, which may allow easier handling or displacement during the battery plate manufacturing process.

[0020] With respect to the conductive properties of the conductive reinforcing mat, the electrically conductive surface of the mat can provide an additional path for the flow of electrons. The path provided by the mat is typically separate from the path provided by the conductive plate or the battery grid. Multiple electron paths (e.g. mat and conductive plate) allows the electrons to flow one or both of the conductive reinforcing mat or conductive plate / mesh, depending on which path provides the least electrical resistance. In this way, when the condition of the electrode deteriorates due to the formation of lead sulfate,

Many electron pathways are maintained, thus extending the overall battery lifetime. In some embodiments, the battery may include a battery separator, which also contains conductive material. The battery separator can provide special electron flow paths in addition to fiber mat and conductive mesh or plate. Such a separator can be particularly useful in the AGM batteries discussed here. In some embodiments, the separator may include a non-conductive separation layer.

[0021] The conductive reinforcing mat also provides excellent reinforcement of the plate or electrode due to their excellent strength properties. The conductive reinforcing mat can also have a relatively small or decreasing mat size. Mats with relatively thin fibers reduce the overall volume that is occupied by the mat, which allows the use of an increased amount of electrolyte and / or paste of active material in a lead-acid battery. The thinner mat also improves the processing efficiency by increasing the mat coverage on the processing rollers, which reduces the frequency of roller changes. In some embodiments, the conductive reinforcing mat may have a thickness of less than 254 μm (10 mils, i.e. 0.010 inches), and usually less than 228.6 μm (9 mils, i.e. 0.009 inches). In one embodiment, the conductive reinforcing mat has a thickness of 152.4 μm (6 mils) and 203.2 μm (8 mils) or between 152.4 μm (6 mils) and 177.8 μm (7 mils).

[0022] In some embodiments, the conductive reinforcing mat may include a combination of electrically insulating fibers and a conductive material. A mat made of these electrically insulating fibers can have an electrical resistance greater than 1 million ohms per square (sheet resistance). In one embodiment, the electrically insulating fibers may include glass fibers, polyolefin fibers, polyester fibers and the like. For convenience in describing the embodiments, the disclosure will mainly describe glass fibers, although it will be appreciated that other electrically insulating fibers may be used.

[0023] The electrically conductive material may comprise a layer or mat of conductive fibers or a layer of other conductive materials, such as sheet metal or foil, which is placed on top of the layer of electrically insulating fibers. In many embodiments, the conductive material is a non-metallic material. In some embodiments, the conductive material may include a coating of conductive material applied to or on the fiber mat. In a specific embodiment, the conductive material may be added to the binder material, which is applied to a plurality of insulating fibers during the production of the fiber mat, or which is sprayed on top of the previously made fiber mat. The conductive material may contain conductive polymers (e.g. polyanilines), carbonaceous material (e.g. carbon black, activated carbon, graphite, carbon nanofibers, carbon nanotubes, graphene, CNS (carbon nanostructure)) and the like. In a specific embodiment, the conductive material may comprise conductive fibers that are distributed at least partially within and / or entangled in a fiber mat having insulating fibers. Conductive fibers can be mixed with insulating fibers (e.g. glass fibers, polymer fibers and the like) to form a mat that is conductive. In an embodiment, graphene or CNS may be used because of them

High electrical conductivity and indifference to sulfuric acid. CNS can be used more widely because it can be easily dispersed in water.

[0024] The conductive reinforcing mat is usually placed in the battery so that the electrically conductive material / layer contacts the active paste of the battery electrodes. The conductive layer mat may be distributed over substantially the entire conductive surface of the reinforcing mat, such that the electrically conductive layer is substantially equal in size and shape to the conductive reinforcing mat. In this way, the electrically conductive layer provides a large conductive surface that contacts the electrode.

[0025] Conductive reinforcing mats may have a total tensile strength of at least 13.61 kg / 7.62cm (30 pounds / 3 inches), and more often at least 15.88 kg / 7.62cm (35 pounds / 3 inches). To achieve this tensile strength, the non-woven fiber mat can have a machine direction tensile strength of at least 9.98 kg / 7.62 cm (22 lb / 3 inches) and a tensile strength in the transverse direction of the machine direction at least 5.9 kg / 7.62 cm (13 pounds / 3 inches). The description "kg / 7.62 cm" ("pounds / 3 inches") generally refers to a method of testing mat strength, where a rectangular piece of 7.62 cm (3 inches) in size 30.48 cm (12 inches) is subjected to stress stretching until the mat is destroyed, such as by tearing or breaking. Mats with tensile strength less than 9.98 kg / 76.2 cm (22 lb / 3 inches) in the machine direction and less than 5.9 kg / 7.62 cm (13 lb / 3 inches) in the transverse direction may not have sufficient strength to withstand winding and rewinding during processing and / or to reinforce lead-acid or other battery plates.

[0026] In some embodiments, the conductive reinforcing mat may comprise a mixture of two or more fibers of different large diameter sizes. The description of large diameter fibers generally includes fibers with a diameter range between 6 μm and 30 μm in one embodiment and between 8 μm and 20 μm in another embodiment. For example, in one embodiment, the conductive reinforcing mat may comprise a blend of first glass fibers having a fiber diameter in the range between 8 μm and 13 μm and second glass fibers having a fiber diameter of at least 6 μm. The preferred diameter range is between 6 μm and 7 μm. Second glass fibers contain sized with silane material to provide increased adhesion and / or acid resistance properties. In one embodiment, the non-woven fiber mats contain at least 25% of each of the first and second glass fibers. Glass fibers usually have fiber lengths that range between 0.85 cm (1/3 inch) to 3.81 cm (1 1/2 inch), although fiber lengths are more often 0.85 cm (1/3 inch) ) up to 1.91 cm (3/4 inch) or 2.54 cm (1 inch).

[0027] Conductive reinforcing mats also contain a binder that binds the glass fibers together and which binds the conductive fibers to the glass fibers when the conductive fibers are used as the conductive material. The binder is usually applied to glass fibers such that the binder constitutes between 5% and 45% by weight of conductive reinforcing mats, between 15% and 35% by weight of conductive reinforcing mats, and more often is between 5% and 30% by weight of conductive reinforcing mats. The binder generally is an acid and / or chemically resistant binder (e.g. acrylic binder), which ensures durability of survival in an acidic environment

EP 2 858 142 B1 throughout the lifetime of the battery and strength for the survival of the paste coating operation. In a specific embodiment, the binder may also contain conductive material. For example, the conductive material (e.g. graphene, graphite powder and the like) may be dispersed in the binder.

[0028] According to one embodiment, the fiber mat (e.g. fiberglass mat) may be coated with a conductive material to form a conductive reinforcing mat. This can be achieved by dip coating, curtain coating, spraying, dipping and extrusion techniques and the like. In another embodiment, the conductive material may be mixed with the binder and applied to the fiber mat during the application of the binder. The latter process represents a "one-step" or single-application process. The binder can help bind the conductive material to the mat. After describing several embodiments of the invention, additional aspects will be more apparent with reference to the figures described below.

[0029] In some embodiments, the conductive material of the reinforcing mat may be non-metallic. A mat coated with a non-metallic conductive material can be used to strengthen the electrode plates and can provide the benefits described herein, such as improving electron permeation and output current, reducing internal resistance, improving charging acceptance and the like. It is believed that by using a mat coated with a non-metallic conductive material either as a separator reinforcing mat or a plate reinforcing mat, electrons do not need to flow through the electrode site where a higher resistance occurs (e.g. due to microcracks and the like). The electrons can flow freely on the conductive surface of the mat and choose a contact point with minimal resistance. This benefit is enhanced after using the battery for an extended period of time.

[0030] In addition to having conductive properties, the reinforcement mats may also provide wick pull-up capability to allow complete wetting of the electrodes. Such mats may also assist in drying the plate / electrode after coating the plate / electrode with a lead paste suspension. The term "wettability" as used herein refers to the ability of the mat to wick up or otherwise transport water and / or other solutions, such as water and acid solution, from a certain place. For example, when testing the wettability or wicking ability of a fiberglass mat, a mat strip, which is often 2.54 cm (1 inch) wide, 15.24 cm (6 inch) long, and typically 0.1-3 mm thick , it can be immersed vertically in water or other solution for a given time, such as 10 minutes. The distance or height at which water in the fiberglass mat is absorbed from the surface of the water or other solution indicates the ability of the mat to wick up or otherwise transport water or solution. The test for determining the average height of the wick pull-up of water by a reinforcing mat can be determined by a method in accordance with ISO8787. In some embodiments, the wick pull-up ability may also improve electrolyte wetting of the electrode.

[0031] The mats described herein increase the wettability of fiberglass mats by adding a wetting component to the fiberglass mats. The wetting ingredient added provides pathways for the evaporation of water and / or water / acid solution. In one embodiment, the wetting ingredient added supports the transport of water and / or water / acid solution to the surface of the mat, where water

And / or the water / acid solution may evaporate. In some embodiments, a combination of first glass fibers, second glass fibers and a wetting component may provide

4-5 times wettability compared to a standard mat.

[0032] In one embodiment, the component added may be a wettable component for an acid-resistant binder that is used to bond the glass fibers of the mat. The wettable component may be a hydrophilic functional group that increases the ability of water and / or water / acid solution to absorb in the glass mat or flow along the surface of the glass mat. In other embodiments, the wettable component may be a hydrophilic binder that is mixed or combined with an acid resistant binder to form a binder mixture. In some embodiments, the wettable component may include starch, cellulose, stabilized cotton, a hydrophilic binder (e.g. acid-based polyacrylic 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 contain only thick glass fibers, or fibers having a fiber diameter between 6 and 30 Pm. The wettable component may increase the ability of such a mat to absorb water and / or a water / acid solution and / or allow water and / or a water / acid solution to flow substantially along the surface of the reinforcing mat.

[0033] The term hydrophilic (or acidophilic) binder as used herein refers to a binder having a contact angle of water (or 33 wt. acid sulfuric acid medium) less than 90 °, preferably less than 70 ° and most preferably less than 50 °. When testing the contact angle of the binder, the binder may be vortex coated on a microscope slide and then cured prior to exposure to the above solution to measure the contact angle. The contact angle measurement is in accordance with ASTM D7334.

[0034] In some embodiments, the binder and wettable component can be added to the mat up to 20% LOI (loss of ignition, and loss on ignition). In other embodiments, a first binder that does not contain a wettable component may be used to bond thick glass fibers, and a second binder having a wettable component (e.g. hydrophilic functional group) can be applied to the mat to increase the wettability of the mat. The first and second binder can be mixed or combined to form a single binder mixture that is applied to thick glass fibers.

[0035] In another embodiment, the wetting component added may be a fiber. The fiber may be a natural fiber, such as cellulose or stabilized cotton, or it may be a synthetic fiber, such as a polyester, or it may contain a mixture of natural and / or synthetic fibers (hereinafter referred to as component fibers). Stabilized cotton contains cotton filaments that are coated with an acid resistant binder and / or embedded in such a binder. Component fibers may have a microfiber structure, or in other words may have fiber diameters between 0.01 and 10 μm, more usually between 0.5 and 3 μm. The ability to wick up or wet component fibers may be better than that of glass fibers (e.g. thick fibers in the range of 6-30 μm) due to the size of the fibers (e.g. microfibers) and / or because the component fibers usually contain hydrophilic functional groups such as OH groups, COOH groups and the like.

[0036] In some embodiments, the component fibers may be formed into a mat that is separate from the fiberglass mat, such as by applying the component fibers to the top of the glass fiber mat. The component fiber mat can be bonded to the glass fiber mat so that the resulting mat will have two layers - a glass fiber layer and a component fiber layer. In some embodiments, the second component fiber mat can be bonded to the opposite side of the fiberglass mat, such that the resulting combined mat has essentially three layers - a glass mat sandwiched between two component fiber mats. In another embodiment, the component fibers may be mixed with glass fibers, such that the resulting mat comprises a combination of entangled glass fibers and component fibers. The acid-resistant binder can be used to bond a component fiber mat to a glass fiber mat, or can be used to bond entangled glass fibers and component fibers to form a reinforcing mat.

[0037] In one embodiment, the glass fiber mat may comprise mainly coarse fibers, or fibers having a fiber diameter between 6 and 30 Pm. Hence, the term "thick" within the preferred meaning of the present invention means that glass fibers having a fiber diameter below 5 μm are not present. In some embodiments, other acid-resistant fibers may be used instead of glass, including polyethylene fibers, polypropylene fibers, polyester fibers and the like. Component fibers (e.g. cellulose fibers) provide a reinforcing mat with good wetting properties by supporting the transport of water and / or water / acid solution to the surface of the reinforcing mat where water and / or water / acid solution may evaporate.

[0038] In another embodiment, the glass fiber mat may contain mainly glass microfibers, or fibers having a fiber diameter between 0.01 and 5 μm. The resulting reinforcing mat may contain mainly or only glass microfibers which are entangled with component fibers or which are bonded to a mat (s) of component fibers. Such a reinforcing mat can have exceptional wetting or wick-up properties.

[0039] In some embodiments, the reinforcing mat may include a combination of thick acid-resistant fibers (e.g. fibers having a fiber diameter between 6 and 30 μm), acid-resistant microfibers (e.g. fibers having fiber diameters between 0.01 and 5 μm) and component fibers. Acid-resistant thick fibers and microfibers are usually glass fibers, although other acid-resistant fibers can be used. In some embodiments, the reinforcing mat may contain between 15-85% combination of thick glass fibers and microfibers and between 1585% component fibers. In another embodiment, the reinforcing mat may contain between 40-60% thick glass fibers, 20-30% glass microfibers and 20-30% component fibers. Component fibers and microfibers can function synergistically to pull up water and / or a water / acid solution, and hence can significantly improve the wettability / pullup ability of the wick reinforcement mat. For example, glass microfibers are typically more wettable than thick glass fibers. However, the microfibers can be covered or hidden by

Thick glass fibers and / or binder, and thus not exposed to water and / or a water / acid solution.

[0040] In some embodiments, a binder having a wettable component (e.g. hydrophilic functional group), for binding a reinforcing mat that contains thick glass and component fibers or which contains thick glass fibers, glass microfibers and component fibers. The wettable component may further increase the wettability of the reinforcing mats, such as by providing another pathway for transporting water and / or a water / acid solution and / or by increasing the exposure of glass microfibers to water and / or a water / acid solution.

[0041] In another embodiment, the wetting ingredient added may be a wettable solution that is added to the reinforcing mat. The wettable solution may be added to the reinforcing mat to saturate the reinforcing mat, or to arrange it on at least one surface of the reinforcing mat after drying the wettable solution. The wettable solution may contain a starch solution, a cellulose solution, a polyvinyl alcohol solution, a polyacrylic acid solution and the like. The wettable solution can be added to the mat after the mat has been formed, such as by dip coating the reinforcing mat in a wettable solution or by applying the wettable solution by spray coating, curtain coating and the like. After application of the wettable solution, the wettable solution can be dried to provide a path for evaporation of water and / or water / acid solution. The wettable solution may then dissolve when exposed to an acidic environment, such as the electrolyte environment of the battery, such that the reinforcing mat still adheres to the electrode after the wettable solution has dissolved.

[0042] According to any of the embodiments described herein, the addition of a wetting component to the reinforcement mat may increase the wettability of the reinforcement mat, such that the reinforcement mat exhibits an average wick pull-up height of at least 1 cm when exposed to water for 10 minutes. The test for determining the average height of the wick pull-up of water by a reinforcing mat can be determined by a method in accordance with ISO8787. Similarly, the addition of a wetting component to the reinforcing mat may allow the reinforcing mat to exhibit an average wicking height of the wicked water / acid solution of at least 1.0 cm after being exposed to the water / acid solution for 10 minutes. This test is similarly carried out in accordance with ISO8787. In other embodiments, the average height of the wick pull-up of the water and / or the height of the wick pull-up of the water / acid solution may be at least 0.8 cm after exposure to the respective solution for 10 minutes. In yet other embodiments, the average height of the wick pull-up of the water and / or the pull-up of the water / acid solution can be greater than 1 cm after exposure to the respective solution for 10 min. As briefly described above, the addition of silane-bonded glass microfibers to the reinforcing mat can significantly increase the wettability / wick-up capacity of the reinforcing mat, such that the average height of the wick water wicking and / or the height of the wick water / acid solution increases.

APPLICATION FORM

[0043] Fig. 1 and 2, respectively, are an exploded perspective view of the lead-acid battery cell 200 and the cross-section of the lead-acid battery cell 200. Lead-acid battery cell 200 may represent the cell used in open-type lead-acid batteries or batteries with glass absorbent mat (AGM). Each cell 200 can provide an electromotive force (emf) of about 2.1 volts, and a lead-acid battery can contain 3 such cells 200 connected in series to provide an emf of about 6.3 volts, or can contain 6 such cells 200 connected in series, to provide an emf of about 12.6 volts and so on. The cell 200 includes a positive plate or electrode 202 and a negative plate or electrode 212 separated by a battery separator 220 so as to electrically isolate the electrodes 202 and 212. Positive electrode 202 includes a mesh or conductor 206 of lead alloy material. Positive active material 204, such as lead dioxide, is usually applied or spread on mesh 206. The grid 206 is also electrically connected to the positive terminal 208. Mesh 206 provides structural support for positive active material 204 along with electrical conductivity to terminal 208.

[0044] Similarly, the negative electrode 212 comprises a mesh or conductor 216 of lead alloy material that is coated or coated with negative active material 214, such as lead. The grid 216 is electrically connected to the negative terminal 218. Like the mesh 206, the mesh 216 supports the construction negative active material 214 along with providing electrical conductivity to terminal 218. In open-type lead-acid batteries, positive electrode 202 and negative electrode 212 are immersed in an electrolyte (not shown), which may contain a solution of sulfuric acid in water. In AGM lead-acid batteries, the electrolyte is absorbed and held in the battery separator 220. The battery separator 220 is located between the positive electrode 202 and the negative electrode 212 to physically separate the two electrodes while allowing ion transport and thus closing the circuit and allowing electrical current to flow between positive terminal 208 and negative terminal 218. Separator 220 typically includes a microporous membrane (i.e. black component), which is often a polymer film with low conductivity. The polymer film may contain voids of micro dimensions that allow ionic transport (i.e. transport of ionic charge carriers) through separator 220. In one embodiment, the microporous polymer membrane or film may have a thickness of 50 microns or less, and preferably 25 microns or less, may have a porosity of 50% or 40% or less, and may have an average pore size of 5 microns or less, and preferably 1 micrometer or smaller. The polymer film may contain various types of polymers containing polyolefins, polyvinylidene fluoride, polytetrafluoroethylene, polyamide, polyvinyl alcohol, polyester, polyvinyl chloride, nylon, polyethylene teraphthalate and the like. The separator 220 may also include one or more fiber mats that are arranged adjacent to one or both sides of the microporous membrane / polymer film to reinforce the microporous membrane and / or provide puncture resistance.

[0045] Near the surface of the negative electrode 212 is a non-woven fiber mat 230 (hereinafter referred to as reinforcement mat). The reinforcing mat 230 is partially or completely disposed on the surface of the negative electrode 212 so as to partially or completely cover this surface. As shown in Figs. 3A-3C, a reinforcing mat 230 can be arranged on both

On the surfaces of the negative electrode 212 or may completely envelop or surround the electrode. Similarly, although the reinforcement mat 230 is shown on the outer surface of the electrode 212, in some embodiments the mat 230 can be placed on the inner surface of the electrode 212 (i.e. tiled to separator 220). The strengthening mat 230 strengthens the negative electrode 212 and provides an additional support component for negative active material 214. The additional support provided by the reinforcing mat 230 can help reduce the negative effects of losing particles of negative active material as the active material layer softens due to repeated loading and unloading cycles. This can reduce the deterioration usually experienced due to repeated use of lead-acid batteries.

[0046] The reinforcing mat 230 is often impregnated or impregnated with negative active material 214, so that the reinforcing mat 230 is partly or completely distributed within the layer of active material 214. Impregnating or impregnating the reinforcing mat with active material means that the active material penetrates at least partially into the mat. For example, the reinforcing mat 230 may be completely impregnated with negative active material 214, such that the reinforcing mat is completely buried in negative active material 214 (i.e. completely buried in lead paste). The complete burial of the reinforcement mat 230 in negative active material 214 means that the mat is completely distributed within negative active material 214. In one embodiment, the reinforcing mat 230 can be arranged within the negative active material up to a depth of X of 50.8 μm (i.e. 0.020 inches) from the outside of the electrode 212. In other embodiments, the glass mat 230 may rest on top of negative active material 214, such that the mat is impregnated with a very small amount of active material. Often, the reinforcement mat 230 will be impregnated with negative active material 214 so that the outer surface of the mat forms the outer surface of the electrode 212 or substantially adjacent to it (see reinforcing mat 240). In other words, the active material can completely penetrate into the reinforcing mat 230, so that the outer surface of the electrode 212 is a blend or mesh of active material and fibers of the reinforcing mat.

[0047] As described herein, the reinforcement mat 230 comprises a plurality of glass fibers, an acid-resistant binder that joins together a plurality of glass fibers to form a reinforcing mat. The reinforcing mat 230 may have a surface weight of between 10 and 100 g / m2², more often between 20 and 60 g / m2². The reinforcing mat 230 may be used to reinforce the lead-acid battery plate or electrode and may contain a relatively homogeneous mixture of thick glass fibers that may contain a plurality of first glass fibers having a diameter between 8 and 13 μm and a plurality of second glass fibers having a diameter of at least 6 um. As used herein, relative homogeneity means that the mixture is at least 85% homogeneous. In some embodiments, the relatively homogeneous mixture may constitute between 70-95% of the weight of mat 230. In some embodiments, the homogeneous mixture may also contain 5-30% conductive fibers. For example, conductive fibers having diameters between 6 and 8 μm and having lengths between 8 and 10 mm may be included in the relatively homogeneous mixture. The reinforcing mat 230 also includes an acid resistant binder that binds many first and second ones

Glass fibers together to form a reinforcing mat 230. The reinforcing mat 230 further includes a wetting component that is applied to the reinforcing mat to increase the wettability / wicking ability of the reinforcing mat 230. The wettability / wicking capacity of the reinforcement mat 230 may be increased, such that the reinforcement mat 230 has or exhibits an average water wick pull up height and / or a water / acid wick pull up height of at least 1.0 cm when exposed to the solution 10 minutes, according to a test carried out according to the method according to ISO8787.

[0048] The reinforcing mat 230 may include a conductive material so as to make the reinforcing mat 230 electrically conductive. For example, a conductive layer may be formed on one or both sides of the reinforcing mat 230 by applying conductive material to at least one surface of the reinforcing mat 230 or by the reinforcing mat 230. The conductive layer may be disposed facing the electrode 212 and in contact with it to provide electrical paths along which electrons can flow. The conductive material contacts the electrode 212, more specifically, the active material of the electrode 212 to allow electrons to flow over the surface or through the reinforcing mat 230. The conductive material and / or the reinforcement mat layer 230 may have an electrical resistance of less than 100,000 ohms per square, and more often less than 50,000 ohms per square, so as to or improve the flow of electrons over the surface of mat 230. In some embodiments, the conductive layer of the reinforcement mat 230 can be electrically connected to the negative terminal 218 to provide a path or path for current flow to the terminal 218.

[0049] As described herein, electrons can flow along the reinforcing mat 230 or mesh / conductor 216, depending on which conductive surface provides the electrical path with the lowest electrical resistance. For example, electrons near the clamp 218 can flow along the electrical path of the grid / conductor 216, while electrons distant from the clamp 218 can flow along the electric path of the reinforcing mat 230 due to the accumulation of lead sulfate on the grid / conductor 216 in the remote position.

[0050] In one embodiment, the conductive layer of the reinforcement mat 230 can be formed on the surface of electrically insulating fibers (e.g. glass fibers) by applying a conductive material to the insulating fibers or by spraying a conductive material on the surface of the reinforcing mat 230. In a specific embodiment, the conductive material can be added to the main binder material that is applied to the wet-laid insulating fibers to connect the fibers to each other. The mixture of main binder / conductive material and wet-laid insulation fibers can then be cured such that the conductive material completely covers the reinforcing mat 230 or saturates it to form a conductive layer. In another embodiment, the reinforcing mat 230 can be made in a standard process where a main adhesive without conductive material is applied to wet-laid insulation fibers to connect the fibers to each other. The conductive material can then be dispersed in an auxiliary or diluted binder, which is then applied or sprayed to the surface of the reinforcing mat 230. The reinforcing mat 230 can then be cured so that the conductive material forms a conductive layer over the entire surface or a specific portion of the reinforcing mat 230. In that

In an embodiment, most of the conductive material can be laid on top of the surface of the reinforcing mat 230.

[0051] In another embodiment, the reinforcing mat 230 can be made according to known processes. Then, a catalyst can be added to the surface of the reinforcing mat 230, and metal ions such as copper can grow through the catalyst applied to the surface of the reinforcing mat. In yet another embodiment, the conductive material can be added to the reinforcing mat 230 using chemical vapor deposition processes.

[0052] In lead-acid battery environments, the conductive material used on the reinforcing mat 230 should be relatively corrosion resistant due to the aggressive electrochemical environment of the battery. In some embodiments, the conductive material may contain metal, nanocarbon, graphene, graphite, conductive polymer (e.g. polyanilines) nanocarbons or carbon nanotubes, carbon fibers, copper, titanium oxides, vanadium oxides, tin oxides and the like. In a specific embodiment, the conductive material may contain carbon nanoslabs, such as graphene. Graphene can be added to the main binder or auxiliary / diluted binder as described above and applied to reinforcing mat 230 (e.g. a mat of glass or polyolefin fibers) between 0.012% and 50% by weight, or in some embodiments between 1% and 25% by weight. After curing, the graphene coating forms a conductive layer over the entire surface or a specific part of the reinforcing mat 230.

[0053] In another embodiment, the conductive layer may comprise a conductive fiber mat, film, or screen which is disposed adjacent to the surface of the reinforcing mat 230 or entangled in electrically conductive fibers (e.g. fiberglass) reinforcement mat 230. In one embodiment, the conductive layer may be made by coating or spraying the conductive fibers on the surface of the reinforcing mat 230. In another embodiment, the conductive fiber mat may comprise a plurality of conductive fibers arranged in a non-woven or woven pattern and joined together by an adhesive. The conductive fiber mat may be connected to the reinforcing mat 230 by an adhesive and the like. Electrons can flow along a conductive fiber mat, film or screen, as described herein, and into the negative terminal 218.

[0054] As described briefly above, the reinforcing mat 230 may contain a plurality of electrically insulating fibers, such as glass, polyolefin, polyester and the like, which are generally used to reinforce the electrode. Because the reinforcing mat 230 is made of such insulating fibers, the reinforcing mat 230 may be substantially non-conductive before or without the addition of conductive material. For example, without joining or adding a conductive material / layer, the reinforcing mat 230 may have an electrical resistance greater than 1 megohm per square. In the course of making the reinforcing mat 230, water or other liquid may be removed (e.g. under vacuum) from a suspension of fibers in a liquid medium. Then, a binder can be applied to the wet laid non-woven glass or polyolefin fibers to form a reinforcing mat 230. As described previously, in some embodiments, conductive material or fibers may be added to the binder and / or liquid medium. In one embodiment, the mat

The reinforcement 230 may have a thickness between 50 microns and 500 microns and have an average pore size between 5 microns and 5 millimeters.

[0055] The reinforcement mat 230 also includes a wetting component that is applied to the reinforcement mat to increase the wettability / wicking ability of the reinforcement mat. The wettability / wicking capacity of the reinforcement mat 230 is increased, such that the reinforcing mat has or exhibits an average water wick height and / or an average water / acid wick height of at least 0.5 cm when exposed to the solution minutes, according to a test conducted in accordance with ISO8787.

[0056] As described herein, the wetting component may be a wetting component of an acid resistant binder (e.g. hydrophilic functional group), a hydrophilic binder that is mixed with an acid-resistant binder, the wetting component may be component fibers (e.g. cellulose or natural fibers) that are bonded to the glass fibers of the reinforcing mat 230, or the wetting component may be a wetting solution (e.g. starch or cellulose solution), which is applied to the reinforcing mat 230, such that the wetting solution saturates the reinforcing mat 230 or is disposed on at least one surface of the reinforcing mat 230 after the wetting solution has dried. In some embodiments, the wetting component may comprise a combination of any of the above-mentioned components, such as a combination of cellulose fibers and an acid-resistant binder having a wettable component. In a specific embodiment, the glass fibers of the reinforcement mat 230 comprise first fibers having fiber diameters between 6 μm and 30 μm or 8 μm and 12 μm and second fibers having fiber diameters of at least 6 μm.

[0057] As described herein, in some embodiments, the wetting component may be a wetting component of an acid resistant binder (e.g. hydrophilic functional group) or a hydrophilic binder that is mixed / combined with an acid resistant binder. In other embodiments, the wetting component may be wettable solutions (e.g. starch or cellulose solution) which is applied to the reinforcement mat 230, such that the wettable solution saturates the reinforcement mat 230, or is disposed on at least one surface of the reinforcement mat 230 after drying the wettable solution. In yet another embodiment, the wetting component may be a plurality of component fibers (e.g. cellulose, cotton, other natural fibers, polyester, other synthetic fibers or a combination of natural and / or synthetic fibers) which are associated with the reinforcing mat 230. According to one embodiment, the component fibers may form a component fiber mat that is associated with at least one side of the glass reinforcing mat 230, such that the reinforcing mat 230 has a two-layer mat configuration. In another embodiment, the component fibers may be mixed with the glass fibers so that when the glass mat is formed, the component fibers are entangled with and bound to the glass fibers. In yet other embodiments, the wetting component may be a combination of the wetting components described above (e.g. a binder having a wettable component, a wettable solution and / or a component fiber).

[0058] Referring now to Figs. 3A-C, various configurations of an electrode reinforcement mat are shown. Fig. 3A shows a configuration in which the electrode 300 has a single reinforcing mat

EP 2 858 142 B1

302 disposed on or near the outer surface. As described above, the reinforcement mat 302 may include material and / or a conductive layer so as to allow electrons to flow on the surface and / or through the reinforcement mat 302 to the battery terminal. The reinforcing mat 302 may also include a wetting component as described above to provide mat 302 with improved wetting characteristics. The reinforcing mat 302 may partially or completely cover the outer surface of the electrode 300. Configuration from fig. 3B is similar to that in Fig. 3A, except that an additional reinforcing mat 304 is arranged on the surface opposite or close to the electrode 300, so that the electrode 300 is sandwiched between two glass mats, 302 and 304. One of the two or both reinforcing mats, 302 and 304, may include material and / or a conductive layer to allow electrons to flow to the battery terminal as well as a wetting component. As such, the electrode 300 can be sandwiched between two conductive reinforcing mats 302 and 304. FIG. 3C illustrates a configuration in which a reinforcing mat 306 wraps or surrounds the electrode 300. Although fig 3C shows a reinforcing mat 306 completely surrounding the electrode 300, in many embodiments the top or portion of the mat 306 or part thereof is open. Glass mat 306 may include material and / or a conductive layer as described above to allow electrons to flow, as well as a wetting component.

[0059] Referring back to Fig. 1 and 2, a reinforcing mat 240 is located near the surface of the positive electrode 202. The reinforcement mat 240 may be arranged and / or connected to the positive electrode 202 similar to the arrangement and connection of the reinforcement mat 230 relative to the negative electrode 212. For example, the reinforcing mat 240 may be distributed partially or completely on the surface of the positive electrode 202, such that it partially or completely covers the surface, may be distributed on the inner surface of the electrode 202 (i.e. adjacent to the separator 220) instead of the outer surface configuration shown and / or can be soaked or saturated with positive active material 204, so that the reinforcement mat 240 will be partially or completely distributed within the active material layer 204. Like the reinforcing mat 230, the reinforcing mat 240 also provides additional support to assist in limiting the negative effects of losing positive active material particles due to multiple loading and unloading cycles.

[0060] In some embodiments, the reinforcement mat 240 may include material and / or a conductive layer to allow electrons to flow on the surface and / or through the reinforcement mat 240 to the positive terminal 208 of the battery. In such embodiments, the electrons can flow along the reinforcing mat 240 or mesh / conductor 206, depending on which conductive surface provides the electrical path with the lowest electrical resistance. For example, electrons near the clamp 208 can flow along the electrical path of the grid / conductor 206, while electrons distant from the clamp 208 can flow along the electric path of the reinforcement mat 240. In some embodiments, both the reinforcement mat 230 and the reinforcement mat 240 may include material and / or a conductive layer to allow electrons to flow on or against both mats. Both the reinforcement mat 230 and the reinforcement mat 240 may contain a wetting component as described herein.

[0061] With respect to the reinforcing function of the reinforcing mats 230 and / or 240, in some embodiments, the reinforcing aspects of these mats can be improved by mixing fibers having different fiber diameters. Reinforcing mats 230 and 240 (hereinafter referred to as reinforcement mat 230) may have similar characteristics and compositions and may contain a mixture of two or more coarse fibers of different diameters. In one embodiment, the reinforcing mat 230 comprises a plurality of first coarse fibers having fiber diameters ranging from 6 μm to 13 μm, from 6 μm to 11 μm, or from 8 μm to 13 μm. The first coarse fibers are mixed with a plurality of second coarse fibers having a fiber diameter of at least 6 μm, preferably between 6 μm and 7 μm. In some embodiments, many of the second coarse fibers may include sized with silane material. A mixture of two or more coarse fibers of different diameters results in a mat that is strong enough to support the active material as described above and to withstand various plate making processes while minimizing thickness by the overall size of the mat. Reducing the thickness of the reinforcing mat 230 while maintaining the strength of the mat may be desirable because the reinforcing mat 230 is usually a chemically inactive component and therefore does not contribute to the electrochemical process of the battery. Reducing the volume of the strengthening mat 230 helps to minimize the volume of non-electrochemical components in the battery.

[0062] In one embodiment, the reinforcing mat 230 comprises a blend of 10% to 95% of the first coarse fibers and of 5% to 80% of the second coarse fibers. In another embodiment, the coarse glass fiber mixture may contain between 70% and 95% of the first coarse fibers and between 5% and 30% of the second coarse fibers. In another embodiment, the coarse glass fiber mixture may contain between 40% and 90% of the first coarse fibers and between 5% and 30% of the second coarse fibers. In another embodiment, the reinforcement mat 230 comprises a mixture of from 10% to 20% of the first coarse fibers and from 60% to 80% of the second coarse fibers. In yet another embodiment, the mixture of the first thick fibers and the second thick fibers is approximately equal (i.e. 50% of the first and second coarse fibers).

[0063] The length of thick fibers can also contribute to the overall strength of the reinforcement mat 230 by physical entanglement with adherent fibers or fiber bundles and / or the creation of additional contact points where separate fibers are bonded by the applied binder. In one embodiment, the first and second thick fibers have a fiber length in the range of 0.85 cm (1/2 inch) to 3.81 cm (1 1/2 inch), although the upper limit of 3.18 cm is more common (1 ¼ inch). This length range ensures sufficient strength of the mat, while allowing the fibers to be dispersed in a solution of white water for mat processing applications. In another embodiment, the first and second thick fibers have fiber lengths in the range of 1.27 cm to 1.91 cm (1/2 to 3/4 inches). The fiber lengths of the first thick fibers may be different from the fiber lengths of the second thick fibers. For example, in one embodiment, the first fibers may have an average fiber length 0.85 cm (1/3 inch), while the second coarse fibers have an average fiber length 1.91 cm (3/4 inch). In one embodiment, one or both the first or second coarse fibers have an average fiber length of at least 0.85 cm (1/3 inch) while in

In another embodiment, one or both first or second coarse fibers have an average fiber length of at least 1.27 cm (1/2 inch).

[0064] The type and amount of binder used to bond the first and second coarse fibers together may also contribute to the overall strength and thickness of the reinforcement mat 230. As described above, the binder generally is an acid and / or chemically resistant binder that provides durability in the acid environment over the lifetime of the battery, durability of the paste coating operation, and permeability to allow paste penetration. For example, the binder may be an acrylic binder, melamine binder, UF binder or the like. The binder may also contain and bind conductive material to the first and / or second thick fibers. Increased use of the binder can limit the thickness of the reinforcement mat 230 by forming more fiber bonds and thickening the reinforcement mat 230. Increased fiber binding may also reinforce the reinforcing mat 230. In one embodiment, the binder is applied to the first and second coarse fibers such that the binder constitutes between 5% and 45% by weight of the reinforcing mat 230 or between 15% and 35% by weight of the reinforcing mat. In another embodiment, the binder is applied to the first and second coarse fibers such that it constitutes between 5% and 30% by weight of the reinforcing mat 230.

[0065] As described herein, the conductive material can be mixed with the binder or auxiliary binder and applied to the first and / or second thick fibers during the production of the reinforcing mat 230 or later. For example, the binder may contain conductive fibers (e.g. carbon fibers) and / or conductive material (e.g. graphite). In some embodiments, the binder may contain between 5-30% graphite particles. The resulting reinforcing mat 230 may have an electrical resistance of less than 100,000 ohms per square, and more often less than 50,000 ohms per square, to allow electrons to flow on or through the surface of the reinforcing mat.

[0066] The wetting component may in some embodiments be mixed with a binder. The resulting reinforcing mat 230 may have or exhibit an average wick-up height of water of at least 0.5 cm when exposed to water for 10 minutes when tested by a method according to ISO8787. The wetting component is soluble in the acid solution of the lead-acid battery, so that a significant portion of the non-woven fiber mat is lost due to the dissolution of the wetting component. For example, 5-85% of the weight of the reinforcing mat 230 may be lost.

[0067] The reinforcement mat 230 configurations described above provide mats having a total tensile strength of at least 13.61 kg / 7.62 cm (30 pounds / 3 inches), and more often at least 15.88 kg / 7.62 cm (35) pounds / 3 inches). The reinforcing mat 230 in particular has a machine tensile strength of at least 9.98 kg / 7.62 cm (22 lb / 3 inches) and a lateral tensile strength of at least 5.9 kg / 7.62 cm (13 pounds) /all). The mats described above have been found to have sufficient strength to support the active material and to withstand various stresses exerted during the manufacture and processing of the plate or electrode (e.g. spreading paste and applying active material). The reinforcing mat 230, which does not have the tensile strength attributes described above, may not be strong enough to support the applied active material (e.g. prevent loss and the like) and / or

EP 2 858 142 B1 may create processing problems, such as breaking the mat when applying an active material paste (e.g., lead or lead oxide) to the glass mat during the plate reinforcement process.

[0068] In addition, the reinforcement mat 230 configurations described above provide mats that are 254 μm (10 mils) or smaller (e.g. 0.010 inches), and more often 228.6 μm (9 mils) or smaller (0.009 inches). In one embodiment, the reinforcing mat 230 has a thickness in the range between 152.4 and 203.2 μm (6 and 8 mils, i.e. 0.006 and 0.008 inches), preferably 177.8 μm (7 mils). These mats take up minimal space around the electrode and the interior of the battery, which allows the battery to contain additional chemically active materials (e.g. additional electrolyte and / or lead paste or lead oxide), thus increasing the efficiency of the battery. The mats described above have a unique combination of both minimum size and strength, while being electrically conductive. These mats also have pore sizes that are in the range between 50 microns - 5 mm.

[0069] In some embodiments, the separator 220 may have a similar composition to the reinforcing mat 230 and may be particularly useful in AGM batteries. For example, the separator 220 may be made of glass fibers or various polymers such as polyethylene, polypropylene and the like. In some embodiments, the separator 220 may include non-woven fibers. The separator 220 may be a non-woven fiber mat. In some embodiments, the reinforcing mat 250 may be placed adjacent to the separator 220. The separator 220 may have a surface weight between about 100 and 400 g / m2². More often the separator 220 has a surface weight between 150 and 300 g / m2². Separator 220 can be a mat formed from a combination of thick glass fibers. For example, the separator 220 may comprise a mixture between 10-20% of many first glass fibers having diameters in the range of 8 to 13 μm and between 60-80% of many second glass fibers having diameters of at least 6 μm. Many second glass fibers may contain sized silane material. The separator 220 may also include an acid resistant binder that binds the first and second plurality of glass fibers to form the separator 220. The binder may be an acrylic binder, melamine binder, UF binder or the like. In some embodiments, the separator 220 may contain between 70-95% of a mixture of thick glass fibers. In some embodiments, the separator 220 may contain 5-30% acrylic binder.

[0070] In some embodiments, the reinforcing mat 250 may also include material and / or a conductive layer to allow electrons to flow on the surface and / or through the reinforcing mat 250 to the positive terminal 208 and / or the negative terminal 218. For example, the fiber mat or mats of the reinforcing mat 250 may comprise a material and / or a conductive layer, such as within a mat binder, as a film, mat or layer of conductive fibers and / or according to any of the embodiments described herein. For example, the binder may contain conductive fibers (e.g. carbon fibers) and / or other conductive materials (e.g. graphite). In such embodiments, the electrons can flow along the reinforcement mat 230, mesh / conductor 216, reinforcement mat 240, mesh / conductor 206, separator 220 and / or reinforcing mat 250, depending on which conductive path provides the least electrical resistance. For example, electrons close to the grid / conductor 216 can flow along the grid / conductor 216 and / or the reinforcing mat

EP 2 858 142 B1

230 to terminal 218, while electrons close to separator 220 flow along electrical path of separator 220 to terminal 218. Similarly, electrons near the grid / conductor 206 can flow along the grid / conductor 206 and / or the reinforcement mat 240 to terminal 208, while the electrons near the separator 220 flow along the electrical path of the separator 220 to the terminal 208. In such embodiments, the available or possible electron paths can be significantly increased. In embodiments where the separator comprises conductive materials, there is a non-conductive layer and / or other non-woven non-conductive mat disposed opposite the conductive part of the separator. In embodiments that do not use another non-woven non-conductive mat, the conductive material in the separator may be disposed on or near the surface of the separator such that at least one non-conductive layer is disposed through the center of the separator.

[0071] In some embodiments, the reinforcing mat 250 may also include a wetting component. For example, the reinforcing mat 250 may contain 10-40% cotton fibers, such as cotton microfibers having diameters between 0.5 and 3.0 μm. The wetting component may increase the wettability / wicking capacity of the reinforcing mat 250 such that the reinforcing mat 250 has or exhibits an average water wick pull up height and / or a water / acid wick pull up height of at least 1.0 cm after being exposed to the solution minutes according to the test performed in accordance with ISO8787.

Processes and methods [0072] Referring now to Fig. 4, a method 400 for producing an electrode is shown. This method may involve transporting a lead alloy mesh 410 on a conveyor toward the active material applicator 430 (e.g. lead paste or lead oxide applicator), which applies or spreads active material 430 onto the 410 mesh. A roll of non-woven mat 420 may be located below the mesh 410, so that the reinforcing mat is applied to the bottom surface of the mesh 410. The reinforcing mat may include a material and / or a conductive layer as well as a wetting component as described herein. In some embodiments, the reinforcing mat may also include a coarse fiber blend as described herein. In some embodiments, the reinforcing mat may also include a blend of thick fibers and glass microfibers in addition to the wetting component as described herein. A second roll of non-woven mat 440 may be located above the mesh 410, so that a second reinforcing mat is applied to the upper surface of the mesh 410. The second reinforcing mat may also contain a conductive material, wetting component and / or a layer and / or a mixture of thick fibers and / or microfibers (similar or different to the reinforcing mat 420). The electrode or plate 450 obtained can then be cut to length with a plate knife (not shown). As described herein, the active material 430 can be applied to the grid 410 and / or to the top or bottom of the reinforcement mats, 440 and 420, so that the active material soaks or saturates the mats to the desired degree. The electrode or plate 450 can then be dried with a dryer (not shown) or other component of method 400. As described herein, reinforcement mats 440 and 420 may assist in drying the electrode or plate 450 by wicking the water and / or

A water / acid solution from the electrode or plate 450 so as to allow the water and / or water / acid solution to evaporate.

[0073] Referring now to Fig. 5. shows a method 500 for manufacturing a lead-acid battery plate. At block 510, a mesh of lead alloy material is provided. The mesh of lead alloy material can be either a positive electrode (e.g. mesh / conductor 206) or negative electrode (e.g. battery grid / guide 216). In block 520, an active material paste is applied to the mesh of lead alloy material to form a battery plate or electrode (i.e. negative or positive electrode). At block 530, a non-woven fiber mat is applied to the surface of the active material paste, such that the non-woven fiber mat is distributed at least partially in the active material paste. As described herein, a non-woven fiber mat may contain a plurality of fibers, a binder material that joins the plurality of fibers together, a wetting component and a conductive material disposed at least partially in a non-woven fiber mat so as to contact the active material paste. The wetting component may provide the ability to pull up the wick to allow complete wetting of the lead battery electrodes. The conductive material may be any material described herein and / or a conductive layer that is formed on a non-woven fiber mat. A non-woven fiber mat may have an electrical resistance of less than about 100,000 ohms per square to allow electrons to flow over the surface of the non-woven fiber mat. In some embodiments, the non-woven fiber mat can be disposed in the active material paste between 25.4 μm (0.001 inches) and 508 μm (0.020 inches).

[0074] In some embodiments, the method may also include applying a second non-woven fiber mat to the opposite surface of the active material paste, such that a mesh of lead alloy material is disposed between the two non-woven fiber mats. The second non-woven fiber mat may also contain conductive material that is disposed at least partially in the second non-woven fiber mat so as to contact the active material paste. In some embodiments, the non-woven fiber mat may have a thickness of 228.6 Pm (0.009 inches) or less and / or a tensile strength of at least 13.61 kg / 7.62 cm (30 pounds / 3 inches).

[0075] In some embodiments, the plurality of fibers may comprise a blend of coarse fibers as described above. For example, many fibers may include first fibers having fiber diameters between 8 μm and 13 μm and second fibers having fiber diameters of at least 6 μm. In some embodiments, the binder may include conductive material. The binder can be applied to the mat between 5% and 45% by weight, between 20% and 30% by weight and the like. In some embodiments, the conductive material may comprise a plurality of conductive fibers that are woven into the fibers of a non-woven fiber mat.

[0076] Referring now to Fig. 6, an embodiment of a method 600 for making a non-woven fiber mat for reinforcing a lead-acid battery plate or electrode (hereinafter referred to as reinforcement mat) is shown. The method described herein can be used to produce reinforcing mats for both open-type lead-acid batteries and for separators in AGM batteries. Block 610 provides a lot of glass fibers. The glass fibers can be thick fibers, microfibers or a combination of thick fibers and microfibers. In block 620 on

In many glass fibers, a corrosion resistant binder is applied to join the many glass fibers together to form a reinforcing mat. In block 630, a wetting component is added to the glass fibers and / or reinforcing mat to increase the wettability / wicking ability of the reinforcing mat. As described herein, the wettability / wicking capacity of the reinforcing mat can be increased such that the reinforcing mat has or exhibits an average water wick pull up height and / or a water / acid wick pull up height of at least 0.5 cm after exposure to the respective solution for 10 minutes, according to a test carried out in accordance with ISO8787. The conductive material can be applied to glass fibers and / or a reinforcing mat in block 640. The application of the conductive material may include providing a layer of conductive fibers and / or other conductive materials and arranging the layer on top of the glass mat. The conductive material may also include a coating that is applied to the mat. In some embodiments, the conductive material can be added to the binder that is applied to the fiber mat. In other embodiments, the conductive material may include conductive fibers that are arranged at least partially within the fiber mat and / or woven into it.

[0077] In some embodiments, the application of the wetting component comprises applying an acid resistant adhesive, wherein the acid resistant adhesive comprises a conductive material and / or a wetting component (e.g. hydrophilic functional group, a mixture of hydrophilic and acid-resistant binder and the like) that works to increase the wettability / the ability to pull up the wick non-woven fiber mat. In another embodiment, the application of the wetting component comprises applying a wettable solution (e.g. starch or cellulose solution and the like) onto a reinforcing mat such that the wettable solution saturates the reinforcing mat or is disposed on at least one surface of the reinforcing mat after drying the wettable solution.

[0078] In yet another embodiment, the application of the wetting component comprises binding of multiple component fibers (e.g. cellulose fibers and the like) with many glass fibers of a reinforcing mat. In such embodiments, the reinforcing mat may contain between 40-95% glass fibers and up to 50% cellulose fibers, and more usually between 10-40% cellulose fibers. In a specific embodiment, the reinforcing mat may contain between 60-80% glass fibers and 10-40% cellulose fibers. In yet other embodiments, the application of the wetting component may include applying any combination of wetting components described herein, such as component fibers, wettable solution and / or acid resistant binder having a wettable component.

[0079] In some embodiments, a plurality of glass fibers may comprise first glass fibers having fiber diameters between 8 Pm and 30 Pm. In such embodiments, method 600 may further include providing a plurality of second glass fibers having fiber diameters between 0.01 Pm and 5 Pm and bonding the plurality of second glass fibers to the first glass fibers by means of an acid resistant binder. The addition of second glass fibers may increase the wettability / wicking capacity of the reinforcing mat such that the reinforcing mat has or exhibits an average water wick pull up height and / or a water / acid wick pull up height of at least 1.0 cm after exposure to the respective solution by 10

EP 2 858 142 B1 minutes according to the test carried out in accordance with ISO8787. In some embodiments, the component fibers (e.g. cellulose fibers and the like) may be bonded to a plurality of first glass fibers and to a plurality of second glass fibers. In such embodiments, the reinforcing mat may contain between 40-80% of first glass fibers, 10-50% of second glass fibers and 5-40% of cellulose fibers. In another embodiment, the reinforcing mat may contain between 40-50% first glass fibers, 2030% second glass fibers and 20-30% cellulose fibers.

Examples [0080] Two reinforcing mats were prepared according to the embodiments described herein. Then the resistance of these mats was measured. Methods for producing mats and results are shown below.

1. Reinforcing mat using graphene as the conductive coating [0081] To produce the conductive graphene coating, a suspension mixture was prepared using graphene (xGnP-M-15 from XG Sciences) and acrylic binder (RHOPLEX ™ HA16 from Dow Chemical). The suspension mixture was prepared to contain about 0.5% binder and 1.5% graphene. A spray gun was used to apply this mixture to the glass mat (Dura-Glass® mat PR-9 and B10). The mat was then dried at 125 degrees Celsius for about 1 hour. and cured at 175 degrees Celsius for about 3 min. Then the surface resistance was measured and the results are shown in Table 1 below.

Table 1: Reinforcing mat using graphene as a conductive coating

<td>A sample</td><td>resistance Surface (Kilo-ohms)</td><td>Sample length (cm)</td><td>Sample width (cm)</td><td>resistance Surface (Kilo-ohms / square)</td><td>Weight before coating (g)</td><td>Graphene %</td>

<td>B-10 (1)</td><td>1.84</td><td>14.3</td><td>12.2</td><td>1.6</td><td>.7609</td><td>15.8%</td>

<td>B-10 (2)</td><td>3.41</td><td>14.2</td><td>12.2</td><td>2.9</td><td>.7643</td><td>14.5%</td>

<td>B-10 (3)</td><td>2.25</td><td>14.2</td><td>11.9</td><td>1.9</td><td>.7334</td><td>17.3%</td>

<td>PR-9 (1)</td><td>13.76</td><td>14.2</td><td>12</td><td>11.6</td><td>.4577</td><td>10.1%</td>

<td>PR-9 (2)</td><td>18.26</td><td>14.2</td><td>12.3</td><td>15.8</td><td>.4651</td><td>11.7%</td>

<td>PR-9 (3)</td><td>5.29</td><td>14.7</td><td>12.2</td><td>4.4</td><td>.4728</td><td>8.9%</td>

[0082] Thanks to the use of graphene material, no significant loss of coating was observed after the standard acid test (40 wt. sulfuric acid, 70 degrees Celsius for 72 hours). As such, graphene-coated glass mat experiences similar weight loss as uncoated glass mats. However, after exposing the glass mat to sulfuric acid for a longer period of time, a slight decrease in conductivity was observed. This slight decrease in conductivity may indicate a reaction between graphene and sulfuric acid.

2. Reinforcing mat using CNS (carbon nanostructure) as a conductive coating [0083] To produce a conductive CNS coating, a slurry mix was prepared using CNS (from Applied Nanostructured Solutions LLC) and / or an acrylic binder (RHOPLEX ™ HA-16 from Dow Chemical) . The suspension mixture was prepared to contain about 1%

EP 2 858 142 B1 binder (or no binder) and 0.5% CNS. The glass mat (Dura-Glass® PR-9 mat or uncoated molded mass mat) was placed in the mixture and the water removed under reduced pressure. A homogeneous CNS coating was obtained. The mat was then dried at 125 degrees Celsius for about 1 hour. and cured at 175 degrees Celsius for about 3 min. Then the surface resistance was measured and the results are shown in Table 2 below.

Table 2: Reinforcing mat using CNS (carbon nanostructure) as a conductive coating

<td>A sample</td><td>resistance Surface (Ohms)</td><td>Length samples (all)</td><td>Length samples (all)</td><td>resistance Surface (Ohms / square)</td><td>CNS%</td><td>Comment</td>

<td>PR-9 (1)</td><td>180</td><td>35.56 (* 4)</td><td>30.48 (12)</td><td>154.3</td><td>2.50%</td><td>With binder</td>

<td>PR-9 (2)</td><td>65</td><td>35.56 (14)</td><td>35.56 (14)</td><td>65.0</td><td>15%</td><td>No binder</td>

<td>PR-9 (3)</td><td>53</td><td>35.56 (14)</td><td>35.56 (14)</td><td>53.0</td><td>25%</td><td>With binder</td>

<td>PR-9 (4)</td><td>50</td><td>35.56 (14)</td><td>35.56 (14)</td><td>50.0</td><td>15%</td><td>No binder</td>

<td>PR-9 (5)</td><td>66</td><td>35.56 (14)</td><td>35.56 (14)</td><td>66.0</td><td>25%</td><td>No binder</td>

<td>Polyester (1)</td><td>239</td><td>34,29 (13.5)</td><td>34,29 (13.5)</td><td>239.0</td><td>0.3%</td><td>With binder</td>

<td>Polyester (2)</td><td>68</td><td>34,29 (13.5)</td><td>34,29 (13.5)</td><td>68.0</td><td>2%</td><td>With binder</td>

<td>Polyester (2)</td><td>132</td><td>34,29 (13.5)</td><td>34,29 (13.5)</td><td>132.0</td><td>0.66%</td><td>With binder</td>

[0084] Due to the use of the CNS material, no significant loss of coating was observed after the standard acid test (40 wt. sulfuric acid, 70 degrees Celsius for 72 hours). As such, the CNS coated glass mat experiences similar weight loss as uncoated glass mats. In addition, after exposure of the glass mat to sulfuric acid for an extended period of time, no significant decrease in conductivity was observed. It is believed that as the CNS has the structure of a "crosslinked matrix of carbon nanotubes", even despite attacking a certain amount of carbon by sulfuric acid, the entire structure remains connected, and therefore the conductivity of the coating is not affected. Given these results, CNS may be a better choice as a conductive coating than graphene. In addition, the CNS coating provides much better conductivity (i.e. lower resistance) than graphene on non-woven mats. For example, as shown in Table 1, for graphene resistance, kilohm units were used, while in Table 2, ohms were used for CNS resistance.

[0085] Several reinforcing mats were prepared according to the embodiments described herein and tested to determine the wettability / wick-up ability of these mats. The wettability / wick-up capacity was tested according to ISO8787. The mats were exposed to both an aqueous solution and a water / acid solution, where the sulfuric acid concentration was about 40%. The test results are shown in Table 3 below.

EP 2 858 142 B1

Table 3: Sample of a reinforcing mat

<td>Sample No.</td><td>Description of the sample</td><td>Binder</td><td>Average height of wick water pulling up after 10 min. (Cm)</td><td>Deviation standard</td><td>Average height of wick acid pull up (40%) after 10 min. (Cm)</td><td>Deviation standard</td>

<td>Checklist</td><td>100% thick glass fibers</td><td>Rhoplex ™ HA-16</td><td>0.0</td><td>0</td><td>0.0</td><td>0.0</td>

<td>1</td><td>50% 3/4 ”K249 T, 50% cellulose</td><td>Rhoplex ™ HA-16</td><td>0.8</td><td>0.15</td><td>1.2</td><td>0.12</td>

<td>2</td><td>50% 3/4 ”K249 T, 50% cellulose</td><td>Hycar® FF 26903</td><td>0.9</td><td>0.15</td><td>0.9</td><td>0.15</td>

<td>3</td><td>50% 3/4 ”K249 T, 25% cellulose, 25% 206-253</td><td>Hycar® FF 26903</td><td>2.7</td><td>0.05</td><td>1.9</td><td>0.25</td>

[0086] A control mat was also prepared and tested to provide a comparison or reference point for the other mats tested. The control mat contains 100% thick glass fibers (T glass fibers) having an average fiber length of about 1.91 cm (3/4 ") and an average fiber diameter of about 13 μm. The glass fibers were bonded together with an acid-resistant binder sold by Dow Chemical under the trade name RHOPLEX ™ HA-16. The acid-resistant binder was applied so that the resulting burn loss (LOI) was approximately 20%. The control mat showed an average wicking height of water and an average wicking height of about 0.0 cm after exposure to the respective solution for 10 minutes.

In other words, the control mat showed essentially no wettability / wick-up ability.

[0087] The first mat (i.e. Sample No. 1) was prepared so that it contained about 50% thick glass fibers having an average fiber length of about 1.91 cm (3/4 ") and an average fiber diameter of about 13 μm, and so that it contained 50% cellulose fibers having an average fiber length about 2.40 mm. Cellulose fibers were made from fibrous pulp by pre-soaking the sulphate cellulose board in water (e.g., Kamloops Chinook sulphate cellulose board manufactured by Domtar) and mixing the soaked sulphate cellulose board in water for at least 10 minutes. Then, the pulp suspension of cellulose fibers was combined with glass fibers. Thick glass fibers and cellulose fibers were bonded together with the RHOPLEX ™ HA-16 binder so that it had

LOI of about 20%. The first mat showed an average wick-up height of 0.8 cm with a standard deviation of 0.15 after exposure to the aqueous solution for 10 minutes. The first mat also showed an average wicking height of the water / acid solution of about 1.2 cm with a standard deviation of 0.12 after exposure to the aqueous solution for 10 minutes.

[0088] A second mat (i.e. Sample No. 2) was prepared so that it contained about 50% thick glass fibers and 50% cellulose fibers having fiber properties similar to the first mat. Thick glass fibers and cellulose fibers were bonded together with an acid-resistant binder sold by Lubrizol under the trade name Hycar® FF 26903. The adhesive was applied so that an LOI of about 20% was obtained. The second mat showed an average wick water height of about 0.9 cm with a standard deviation of 0.15 after exposure

Aqueous solution for 10 minutes. The second mat also showed an average wicking height of the water / acid solution of about 0.9 cm with a standard deviation of 0.15 when exposed to the aqueous solution for 10 minutes.

[0089] A third mat (i.e. Sample No. 3) was prepared so that it contained about 50% thick glass fibers and 25% cellulose fibers having fiber properties similar to those of the first and second mats. The third mat also contained about 25% glass microfibers having an average fiber diameter of about 0.76 μm (i.e. Johns Manville 206-253 fibers). Thick glass fibers, glass microfibers, and cellulose fibers were bonded together with the Hycar® FF 26903 binder so that it had an LOI of about 20%. A third mat showed an average wick water height of about 2.7 cm with a standard deviation of 0.05 after exposure to an aqueous solution for 10 minutes. The third mat also showed an average wicking height of the water / acid solution about 1.9 cm with a standard deviation of 0.25 when exposed to the aqueous solution for 10 minutes.

[0090] As shown in the test results above, the addition of a wetting component to the reinforcing mat, which in this case contained cellulose fibers, significantly increased the wettability / wicking capacity of the reinforcement mat. In addition, the inclusion of glass microfibers in the reinforcing mat in addition to the wetting component significantly increased the wettability / wicking capacity of the reinforcing mat beyond that shown by the addition of the wetting component alone.

[0091] Where a range of values ​​is depicted, it is understood that any value within this range, to the nearest tenths of the lower limit unit, unless the context clearly dictates otherwise, between the upper and lower limits of the range is also specifically disclosed. Any smaller range between a given value or a value within the given range and any other given value or within a given range is included. The upper and lower limits of these smaller compartments may independently be included or excluded from the compartments, and any compartment in which any of the two, none of the two or both limits are included in the smaller compartments are also included in the invention, excluding any specifically excluded limit value in the given range. Where the range given includes one or both of the limits, the exclusion ranges of either of the two or both of these covered values ​​are also covered.

[0092] As used in the appended claims, the singular forms of indefinite English articles "a", "an", and the specific "the" (in the original language) include plural references, unless the context dictates otherwise. Hence, for example, reference to "method" includes many such methods, and reference to "device" includes reference to one or more devices and their equivalents known to the skilled person, and so on.

[0093] In addition, the words "comprises", "comprising", "include", "including" and "includes" when used in this specification and in the claims below are intended to indicate the presence of the following characteristics, integers, components or steps, but they do not exclude the occurrence or addition of one or more other characteristics, integers, components, steps, activities or groups.

EP 2 858 142 B1