KR101141450B1 - Seperator material for forming a separator for an acid accumulator - Google Patents

Abstract

The present invention relates to a separator material (6) for forming a separator for lead-acid batteries, in particular in the form of an unfinished roll product, and a method of making the same. The separator material 6 of the invention comprises a first layer in the form of a microporous membrane 1 and at least one second layer in the form of a planar fleece material 7. At least one side of the microporous membrane 1 composed of thermoplastic material is provided with a plurality of protrusions 2, 2 'which form an area with an increased film thickness on the base membrane sheet. The fleece material 7 is welded to the membrane 1 by ultrasonic welding in such a way that the planar fleece material 7 is at least at the surface level of the base membrane sheet without penetrating into the region of the weld seam 8. do.

Description

Separator material for forming a separator for an acid accumulator

The present invention relates to separator materials for forming separators for lead-acid accumulators and to methods of making such separator materials.

In acid batteries, separators are located between adjacent electrode plates of different polarities, in particular acting as electrical insulators, in order to prevent metallic conduction between the plates in direct contact between the plates. At the same time, however, the separator must allow the flow of ionic current in the electrolyte between the electrodes. To meet these various functions, separators typically comprise a microporous film, for example dendritic growth or electrical short circuits between the plates by particles separating from the plates. The pores of the microporous membrane should be as small as possible to prevent, and the porosity of the microporous membrane should be as large as possible to minimize the internal resistance of the battery. For the same reason, it is also preferred that the separator be as thin as possible in construction.

Such separators are generally made from oxidation-stable materials in the form of thermoplastics that can withstand the active electrolyte beyond the life of the battery. The separator is generally made in the form of a pocket into which a positive or negative electrode plate is inserted, for example by folding and welding at the sides.

In use, oxygen is generated in the positive plates during the charging operation, which can attack the separator material and finally damage the separator material so that a short circuit occurs between the plates. For this reason, in many cases, at least one side of the separator is provided with ribs or raised areas that act as spacers to avoid direct contact of at least the positive electrode plate and the separator base sheet.

Many different arrangements of rib-like spacers are already known in the art. Separators are known that have many vertical ribs that span the entire length of the separator and are located at regular intervals, for example between 6 and 13 mm. Thus, a typical separator for a starter battery includes about 12 to 25 ribs over a width of approximately 160 mm. In the separator of US Pat. No. 5,558,952, continuous ribs have been replaced by discontinuous ribs.

Separator not only fulfills the above-mentioned problems, but also has more functions, which are generally important for the working capacity of the battery. Thus, the chemical composition of the active material of the electrode plate is changed periodically during the charge and discharge cycles of the battery. As a result of these changes and external influences, for example by mechanical shock or vibration, some active materials may fall off, especially in positive plates. In particular, the incidental loss of active material from both electrodes gradually reduces the charging capacity of the battery. Moreover, fallen active material can collect as a sediment at the bottom of the battery cell, resulting in a short circuit between the electrodes with different polarities, especially in the case of sheet separation, leading to rapid failure of the battery. Disadvantages of falling of the active material into a fleece material, such as a glass fiber fleece, a polyester fleece or a fleece of a mixture of polyester and glass fibers, which is located between the microporous membrane and the positive plate and compressed It is known to prevent this. In this way, cycle stability of the battery can be improved.

In document DE 29 24 239 C2, microporous laminated materials are described for use as separators. The laminate material is laminated entirely and thermally bonded into a first layer of microporous thermoplastic or heat-curable, or a second layer of non-woven fiber web composed of 100% polyester fibers. And thermosetting polymeric materials. The laminating is a roll nip in which a polyester fiber web and an extruded microporous material are sandwiched simultaneously in a conventional twin-roll calender. It can form by action. Alternatively, the stack can also be formed in a triple-roll calender. This process is difficult to implement and is not suitable for all purposes. Thus, for example, by laying a polyester fiber net in an easy manner on the side of the microporous material facing the positive electrode while a rib is provided and in use, or by separating one of the two components It is impossible to reuse them. In addition, the polyester fiber net is wider than the separator by the co-extrusion of a separator with several separator widths, which is conventionally used for reasons of saving the separator's trouble-free weldability and fleece material. It is difficult to manufacture this narrow separator. Finally, in order to be bound to the fiber net, the polymeric material must remain, for example, in solution or non-crosslinked, and thus can penetrate into the fiber net when passing through the calender.

Document DE 33 35 547 C1 proposes a weldable flat web material which forms a separator pocket. The net material includes a membrane material in which the fleece material is in the form of a web, for example applied by gluing. The fleece material may be glass fiber fleece or polyester fleece. In order to form pockets by welding on the sides, the sides of the fleece layer are selected so that the edge region of the membrane material is not covered by the fleece.

In order to secure the fleece to a stable, permanent and easy to handle microporous membrane in the manufacturing process, in the prior art the two components are glued together in most cases. Such gluing and in particular the metering of the adhesive to be used has proved difficult to solve. On the other hand, if the amount of adhesive used is too small, there is a risk that the hold of the associated fleece is too low, and if the amount of adhesive used is too high, the adhesive may seep through the fleece, resulting in a separator formed during the next process of manufacture. Rolls stick and become unusable. For this reason, the fleece needs to have a thickness of at least about 0.3 mm (measured with a load of 10 N for a measuring area of 100 cm ² ). It was not possible to use thinner and less expensive materials without loss of quality and economics. Furthermore, if the amount of adhesive used is too large, the electrical resistance of the capacitor increases, and certain adhesives have the disadvantage of contaminating the electrolyte and degrading the electrical characteristics of the capacitor. Mechanical treatment of bonding the fleece to the microporous membrane, such as lamination by calendering mentioned above, or compression welding between two cog wheels, which creates deformation or holes in the membrane, is not an alternative. . This is because a sufficiently high throughput rate cannot be achieved with this method, and a sufficiently strong bonding cannot be achieved by compression welding.

Accordingly, there is a need to provide an improved structure and improved method of combining microporous sheets and fleece materials to form separator materials for forming separators for lead-acid batteries, which are stable, permanent, and easy to handle in the manufacturing process.

In other words, it is an object of the present invention to manufacture a separator comprising a first layer of microporous membrane and a second layer of planar fleece material, thereby eliminating the above mentioned disadvantages by simply making the separator without being expensive.

Still another object of the present invention is to provide a method for producing a separator that is easy to use without limitation.

In order to solve the above problems, the present invention is made of a thermoplastic material, on the at least one side of the base sheet, having a plurality of protrusions located in the center region of the microporous sheet, the first layer in the form of a microporous sheet And at least one second layer in the form of a planar fleece material located on the face of the microporous sheet, the fleece material being coupled to at least some of the plurality of protrusions of the microporous sheet by a plurality of welded seams. Characterized in that a fleece material does not penetrate the microporous sheet, wherein the height of the protrusions is greater than the thickness of the fleece material. To provide a separator material in the form of a web.

The present invention also provides a microporous sheet having a plurality of protrusions, the fleece material of which is made of a thermoplastic material and located on at least one side of the base sheet, located in the central region of the microporous sheet. Providing a step of placing the fleece material on the face of the microporous sheet, and welding the fleece material with the projections of the microporous sheet such that the fleece material is formed by the weld seam of the plurality of projections of the microporous sheet. Allowing at least a portion to bond the fleece material into the microporous sheet, wherein the height of the protrusions is greater than the thickness of the thickness of the fleece material. Provided are methods of making separator materials in the form of a web for forming separators.

According to the present invention, it is possible to provide an improved structure and improved method for combining microporous sheets and fleece materials to form separator materials for forming separators for lead-acid batteries, which are stable, permanent and easy to handle in the manufacturing process. Do.

1 shows a plan view of one side provided with ribs in the cross section of the microporous sheet before applying the planar fleece material.
FIG. 2 shows a cross section of the microporous sheet when a planar fleece material is applied to the microporous membrane along the line II-II of FIG. 1.

According to the invention, the separator material for forming the separator for lead-acid batteries is a planar fleece material and a first layer in the form of a microporous sheet, especially in an unfinished rolled product. It is configured to include at least one second layer. The microporous sheet is made of thermoplastic material and has a plurality of protrusions on at least one side. The protrusions here are rigid and are preferably formed integrally with the basic sheet to form sheet regions of increased thickness. In this combination, the cross-sectional dimension of the microporous sheet perpendicular to the face of the sheet is determined by the sheet thickness away from the protrusion (ie the thickness of the base sheet), the sheet thickness in the area of the protrusion and the height of the protrusion (ie, the sheet in the protrusion area). The difference between the thickness and the sheet thickness away from the projections). The planar fleece material may comprise a nonwoven material that is compatible with an aggressive battery environment. This fleece material is located at least on the face of the sheet with protrusions. If the sheet has protrusions on both sides, the fleece material may be located on either side or on only one side. The fleece material is secured to the sheet by a weld seam between the fleece material and the sheet such that the planar fleece material is at least at the level of the surface of the base sheet in the welded seam area (ie, the level of the sheet surface in the non-projection area) It does not go down. This means that the surface of the planar fleece material facing the sheet is not located below the level of the surface of the base sheet in the region of the weld seam. The weld seam here is made on the sheet face on which the planar fleece material is located. Here, if the planar fleece material is bonded by welding seams to at least some of the protrusions of the sheet, it is preferable that the weld seams are each positioned on the protrusions of the sheet.

This technique according to the invention allows the very thin fleece material, described in detail below, to be fixed to the microporous sheet by ultrasonic welding without the risk of generating weak spots and holes in the microporous sheet. Has an advantage. This advantage results in a very high throughput rate in the production environment, and a smaller amount of fleece, since it is possible to use thin fleece, preferably with a thickness of less than 0.25 mm, in particular between 0.1 and 0.25 mm. Will be needed. Separator materials of the present invention can be made less expensive than materials known in this way.

Preferably, at least some of the protrusions consist of ribs that extend vertically and span the entire length of the separator material and may be discontinuous or continuous. The vertical direction for the separator material in the form of a web is the direction of the web. Here, one of the ribs is preferably erected in one of the side edge regions of the sheet and the fleece material is joined to the sheet at the side of the sheet by a weld seam that runs through the two side ribs. It should be noted here that during the welding process certain ribs under welding may disappear completely so that the fleece material should be at the surface level of the membrane base sheet at the weld seam. In a preferred weld, the weld seam should be as close to the edge of the separator material as possible. However, preferably in terms of the width of these edge portions being between 5.5 and 9.5 mm each, it is preferred not to cover the narrow edge portions of the sheet with a fleece material in order to facilitate pocket formation by welding of separator material. Be careful. The ribs on both sides are preferably continuous ribs. The weld seam is preferably continuous, but may also be discontinuous.

It is also possible that the sheet and the fleece material are only spot-welded with each other.

Preferably, the microporous sheet is made of polyolefin. It is particularly preferred here that the polyolefin has a molecular weight of at least 300,000, and under normal conditions the melt index is substantially zero and has a viscosity of at least 600 ml / g. Suitable polyolefins are polyethylene, in particular polyethylene with a filler content of silica.

It is also preferred that at least 50% of the pores of the microporous sheet have a diameter of 0.5 μm or less. It is also preferable if the microporous sheet has a thickness of 0.1 to 0.6 mm in the portion without protrusions, more preferably 0.15 to 0.25 mm, most preferably about 0.2 mm.

The fleece material may, for example, consist essentially of glass fibers or more preferably consist essentially of polyester fibers. Fleece materials comprising a mixture of glass fibers and polyester fibers are preferred, especially if the content of glass fibers in the mixture does not exceed 70% by weight. They have the advantage of being easy to handle, easy to cut and cleanly cut at the edges. It is further preferred if the fleece material has a thickness of 0.1 to 0.25 mm (measured with a load of 10 N for a measuring range of 100 cm ² ). However, it is also possible to use other fleece materials that are stable in an aggressive environment in batteries and can be welded with microporous membranes.

Such separator materials can be prepared according to the invention by first providing the aforementioned microporous membranes and by providing one of the planar fleece materials described above for each side of the membrane. Planar fleece material or planar fleece materials are placed on the face of the membrane with projections and welded with a number of membrane projections so that the plane fleece material is at least at the level of the membrane base sheet surface at the part of the weld seam and lowered below it. Do not During welding, the protrusions dissolve at least in part so that under certain circumstances these protrusion materials may leave the original protrusion area and cause changes in shape such as, for example, a decrease in protrusion height. Here the fleece material does not need to be completely placed on the sheet before welding. Rather, the microporous membrane and the at least one fleece material may be laid in sections, or may be welded progressively in sections or continuously. In order to obtain a good bond, it is desirable to press the planar fleece material into the projections of the membrane before welding.

Preferably, the welding is performed by ultrasonic welding. Welding by thermowelding is also possible, in which electrical energy is directly converted into the heat required for welding.

In the case of the preferred sheet and fleece materials according to the invention, a processing speed of at least 90 m / min, preferably at least 100 m / min, is allowed and can be processed with a short reaction time without long heating and cooling time. Ultrasonic welding is preferred.

It is further preferred if at least some of the projections of the microporous sheet have a height of 0.5 to 0.6 mm and welding is done on these projections. Here the height of the projections can be reduced during welding.

The fleece material preferably has a thickness of 0.1 to 0.25 mm.

The invention is explained in more detail by the following preferred embodiments with the aid of the drawings.

The microporous membrane (also referred to as microporous sheet, hereinafter used in both terms) shown in the top view of FIG. 1 is a plurality of continuous, vertical in the middle region 4 and distributed at regular intervals along the width. It has ribs 2 and 2 '. In this example, the distance between the ribs is 12.5 mm and eleven ribs are provided. However, the ribs may be more or less and / or may be longer or shorter in distance. In the lateral edge region 5, in each case the membrane 1 has a number of more tightly spaced vertical ribs 3. In this example, the lateral edge region 5 comprises six ribs per cm, but this number may also be larger or smaller.

The number of ribs 3 of the lateral edge region 5 can thus be greater, for example, at least about 10 to 12 per cm, as described in the document EP 0 899 801 A1. However, it is possible to provide fewer ribs 3 or to have the ribs 3 as a whole. Instead of the ribs 3 which are erected in the vertical direction, a plurality of short, vertically spaced horizontal or angled ribs, or documents US 5,588,952, as described, for example, in US 5,716,734. As described, a combination of vertically spaced ribs and vertically spaced ribs they intersect can be provided. Finally, instead of the rib 3, the edge region 5 of increased thickness, for example twice as thick as compared to the center region 4, as described in EP 0 484 295 B1. It is also possible to provide).

* The arrangement and configuration of the ribs 2, 2 'shown in the center region 4 of the microporous sheet 1 are merely shown as examples. Thus, continuous ribs 2, 2 'can be replaced with discontinuous ribs. Document US 5,588,952 shows a discontinuous rib having a length not exceeding 1 cm, preferably not exceeding 0.5 cm, with an intermediate region between sections, at least twice the length of the sections. Alternatively, in addition to the vertical ribs 2, 2 ′, the microporous sheet 1 may have a plurality of continuous ribs that also run in the transverse direction as described in US Pat. No. 5,776,630. have. Document WO 01/13442 describes a number of burl-like studs regularly arranged on at least one face and at least one in the middle region, preferably two to four consecutive, vertical Separator in the form of a microporous sheet with ribs is described. It is preferable to use at least one rib 2 'in each case where it runs preferably continuously perpendicularly to each edge portion of the center region 4 of the microporous membrane (microporous sheet) 1. Do. As already described, any of the embodiments mentioned with respect to the ribs and / or projections in the middle region 4, depending on the properties of the membrane shown in FIGS. It may of course be combined with the embodiments mentioned with respect to the projections. However, the embodiment shown in FIGS. 1 and 2 with continuous ribs 2, 2 ′, 3 standing in the vertical direction in the middle region 4 and the side edge region 5 is preferred.

The microporous sheet 1 is preferred for all microporous sheets according to the invention and is very stable in the active environment of acid batteries, for example from plastics such as polyolefins, polypropylene, polyvinyl chloride or mixtures thereof, Or from other suitable materials. Preferred materials are polyolefins, for example polypropylene, ethylene / butane copolymers, and preferably polyethylene, more preferably polyethylene of high molecular weight, ie polyethylene having a molecular weight of at least 300,000, in particular at least 600,000, even more preferably Ultra-high molecular weight polyethylene, ie at least 1,000,000, in particular at least 4,000,000, more particularly at least 5,000,000 molecular weight [viscometry and Margolie's equation (Hosef Berzen, CZ Chemie-Technik , volume 3 1974, no.4, p.129)], a melting point index of substantially 0 [measured according to ASTM D1238 (Condition E) using a reference load of 2,160 g], Viscosity number of at least 600 ml / g, more preferably at least 1,000 ml / g, even more preferably at least 2,000 ml / g, most preferably at least 3,000 ml / g [100 ml decalin at 130 ° C. Calculated using a 0.02 g polyolefin solution).

The microporous sheet 1 is preferred for all microporous sheets according to the invention, with 8 to 100% by volume of polyolefin, 0 to 40% by volume of plasticizer and 0 to 92% by volume of inert filler material. homogeneous mixture of materials). Preferred fillers are granular silicon dioxide. Preferred plasticizers are oils, in particular mineral oils or process oils obtained therefrom. The plasticizer is suitable for making the membrane porous because it is the component that can be most easily removed from the mixture of polymers, fillers and plasticizers. The final component of the microporous membrane depends on the original mixture and the composition or components extracted. Materials of this type are known and described in the prior art, for example in US Pat. No. 3,351, 495.

The size of the pores of the microporous sheet according to the present invention, such as the microporous sheet 1, is preferably smaller than 1 mu m in diameter. Preferably, at least 50% of the holes have a diameter of 0.5 μm or smaller. Here, it is particularly preferable if at least 90% of the holes have a diameter smaller than 0.7 mu m.

2 shows a cross section through the finished separator material 6, which refers to a cross section through the microporous sheet 1 to which the planar fleece material 7 is applied. The rib 3 in the lateral edge region 5 has a much lower height than the ribs 2, 2 ′ in the middle region 4 of the membrane 1. Although the membrane 1 shown has ribs 2, 2 ′ on only one side, it is also possible that the ribs 2, 2 ′ and / or ribs 3 are also provided on the other side.

The thickness of the base sheet of the sheet 1 is preferably 0.1 to 0.6 mm, more preferably 0.15 to 0.25 mm, and most preferably about 0.2 mm.

In the center region 4 of the sheet 1 the ribs 2 ′ have a height of preferably about 0.3 to 1.3 mm and more preferably 0.4 to 0.9 mm before welding with the planar fleece material 7. Has It is particularly preferred if the height of the ribs 2, 2 'is approximately 0.5 to 0.6 mm. The base width of the ribs is about 0.5 to 1.5 mm and preferably 0.6 to 0.8 mm. In addition to the preferred trapezoidal cross sections shown, the ribs can have any suitable cross section, for example circular, rectangular, triangular cross sections. In these examples, the possible shape and size of the ribs can also be applied to all of the possible ribs mentioned above. For the formation of protrusions suitable in the context of the present invention, it is critical to provide sufficient additional sheet material to enable welding of the sheet and fleece materials without the risk of developing weak spots or holes. In this regard, the additional sheet material can be said that the weld seam is made in a thicker sheet area compared to the base sheet or is almost completely removed from the part of the weld seam after welding, the fleece material being at this level the level of the surface of the membrane base sheet. It does not go down. For welded joints, the proper shape of the projection depends on the material and dimensions of the membrane, the composition and size of the fleece and the chosen welding process, as will be readily apparent to those skilled in the art.

As can be seen in FIG. 2, the planar fleece material 7 is located in the sheet 1. The fleece material 7 is joined to the two outermost ribs 2 ′ by two welding seams 8 that span the entire length of the sheet 1. The weld seam 8 runs along the rib 2 'along its entire length. However, it is also possible to provide discontinuous welding seams along individual spot-welding points. Fleece materials suitable in the context of the present invention are, for example, fleece having a fleece weight of 25 g / m ² , fiber mixtures of 80% PET fibers and 20% PET melt fibers (PET is short for polyethylene terephthalate), fibers Has an average diameter of 3 dtex and an average fiber length of 15 mm.

Here, the fleece material 7 preferably has a thickness of 0.1 to 0.25 mm.

In FIG. 2, the rib 2 ′ has the same height as the protrusion 2. According to the above description, however, welding may occur in which the height of the projection 2 'is reduced in comparison with the projection 2. In this context, the height of the projection 2 'can also be reduced to zero.

Welding is performed by ultrasonic welding. This process allows for a processing speed of at least 90 m / min in a very advantageous way. Thermoplastic microporous membranes with different arrangements of ribs and / or other types of protrusions can be bonded to the fleece material in this manner, and such separator materials are likewise separator materials of the present invention. For example, all of the above mentioned microporous membranes can be used when the welding seam is used in the thick edge region, for example, a microporous membrane having a thick edge region known from EP 0 484 295 B1. have.

Microporous sheet: 1
Fleece Material: 7
Weld seam: 8
Turning: 2, 2 '

Claims (22)

Made of a microporous sheet 1 consisting of polyolefin and having a plurality of protrusions 2, 2 'on at least one side of the base sheet, wherein each of said protrusions forms an increased film thickness. A first layer and at least one second layer in the form of a planar fleece material 7 located on the face of the microporous sheet 1,
The planar fleece material 7 has a thickness from 0.1 mm to 0.25 mm and comprises a polyester fiber or a glass fiber and a mixture of the polyester fiber,
The planar fleece material 7 of the at least one second layer is joined to the microporous sheet 1 by a plurality of welded seams 8, so that the planar fleece material 7 is welded. At least on the surface of the base sheet in the region of the joint 8 so as not to penetrate the base sheet,
The planar fleece material 7 of the at least one second layer is characterized in that it is coupled to at least some of the plurality of projections of the microporous sheet 1 by the weld seam 8, Separator material for forming separators for lead-acid batteries.
delete Separator material according to claim 1, characterized in that the projection (2, 2 ') is a rib (2, 2') extending vertically over the entire length of the separator material (6).
4. The ribs 2, 2 ′ according to claim 3, wherein the ribs 2, 2 ′ in the vertical direction respectively comprise the ribs 2 ′ in both edge regions 5 of the separator material 6. 8) separator material characterized in that the weld seam (8) is connected to the ribs (2 ') at both of these edges.
Separator material according to claim 4, characterized in that the ribs (2 ') of the both edge regions are continuous ribs and the welding seam (8) is a continuous welding seam.
Separator material according to claim 4, characterized in that the ribs (2 ') of the both edge regions are discontinuous ribs and the welding seam (8) is a discontinuous welding seam.
Separator material according to claim 1, characterized in that the weld seam (8) is a spot-welded joint.
delete The separator material of claim 1, wherein the polyolefin has a molecular weight from 300,000 to 9,000,000 and a melting point index of zero under normal conditions.
The separator material of claim 9, wherein the polyolefin is polyethylene.
The separator material of claim 1, wherein the polyolefin is made from polyethylene having a silica filler.
Separator material according to claim 1, characterized in that from 50% to 100% of the pores of the microporous sheet (1) are larger than 0 μm and have a diameter of 0.5 μm or less.
Separator material according to claim 1, characterized in that the microporous sheet (1) has a thickness of 0.1 to 0.6 mm in the region free of the protrusions (2, 2 ').
delete delete delete The separator material of claim 1, wherein the content of the glass fibers in the mixture is greater than 0 wt% and no greater than 70 wt%.
delete (a) a microporous sheet (1) made of polyolefin and having a plurality of protrusions (2,2 ') on at least one side of the base sheet, wherein each of said protrusions has increased sheet thickness and has Steps,
(b) providing at least one planar fleece material (7), wherein the planar fleece material (7) has a thickness from 0.1 mm to 0.25 mm, comprising polyester fibers or glass fibers and the polyester Comprising a mixture of fibers,
(c) placing the at least one planar fleece material 7 on the face of the microporous sheet 1 having the plurality of protrusions 2, 2 ′, and
(d) welding the at least one planar fleece material 7 with at least a portion of the plurality of projections of the microporous sheet 1 such that the planar fleece material 7 is connected to the weld seam 8. And at least on the surface of the base sheet in the region, such that it does not penetrate the base sheet.
20. The method of claim 19, wherein the welding is by ultrasonic welding.
The method of claim 19, wherein the plurality of protrusions have a height of 0.5 to 0.6 mm.
delete

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