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WO2000011746A1 - Separateur pour accumulateurs ou batteries au plomb - Google Patents

Separateur pour accumulateurs ou batteries au plomb Download PDF

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Publication number
WO2000011746A1
WO2000011746A1 PCT/US1999/018499 US9918499W WO0011746A1 WO 2000011746 A1 WO2000011746 A1 WO 2000011746A1 US 9918499 W US9918499 W US 9918499W WO 0011746 A1 WO0011746 A1 WO 0011746A1
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WO
WIPO (PCT)
Prior art keywords
cell
separator
battery
saturation
cells
Prior art date
Application number
PCT/US1999/018499
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English (en)
Other versions
WO2000011746A8 (fr
Inventor
Michel M. Lawrence
Original Assignee
Gnb Technologies
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Filing date
Publication date
Application filed by Gnb Technologies filed Critical Gnb Technologies
Priority to KR1020007004150A priority Critical patent/KR20010031203A/ko
Priority to AU54850/99A priority patent/AU5485099A/en
Priority to EP99941138A priority patent/EP1031170A1/fr
Priority to CA002306691A priority patent/CA2306691A1/fr
Priority to JP2000566913A priority patent/JP2002523880A/ja
Publication of WO2000011746A1 publication Critical patent/WO2000011746A1/fr
Publication of WO2000011746A8 publication Critical patent/WO2000011746A8/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • H01M10/12—Construction or manufacture
    • H01M10/121—Valve regulated lead acid batteries [VRLA]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • H01M50/437—Glass
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • This invention relates to lead-acid cells and batteries and, more particularly, to separators used in making such cells and batteries.
  • a wide variety of applications utilize conventional, flooded electrolyte lead-acid cells and batteries, or sealed lead-acid cells and batteries, often termed VRLA cells and batteries ("valve-regulated lead-acid").
  • the lead-acid cells and batteries provide stand-by power in the event of a power failure.
  • such cells and batteries are maintained at a full state-of-charge and in a ready-to-use condition, typically by floating at a constant preset voltage.
  • Stationary batteries are used for stand-by or operational power in a wide variety of applications, including, by way of illustration, telecommunications, utilities, for emergency lighting in commercial buildings, as stand-by power for cable television systems, and in interruptible power supplies for computer back-up power and the like.
  • VRLA cells can vary widely.
  • such cells are disclosed in U.S. 3,362,861 to McClelland et al.
  • Such cells utilize highly absorbent separators; and the necessary electrolyte is absorbed in the separators and plates.
  • Such cells are normally sealed from the atmosphere by a valve designed to regulate the internal pressure within the cell so as to provide what is termed an effective "oxygen recombination cycle" (hence, the use of the terms “sealed” and “valve-regulated” as well as “recombinant”).
  • Recombinant battery separator materials (sometimes termed "RBSMs”) have traditionally comprised a highly absorbent glass fiber mat.
  • Separators of this type have adequate absorbency to hold the amount of electrolyte desired and possess some vacancy of pores to allow the oxygen recombination cycle to proceed.
  • suitable glass fiber mats are commercially available and are in use in VRLA cells and batteries.
  • Badger discloses a separator having, in general, two types of fibers.
  • a first set of fibers imparts to the separator an absorbency greater than 90% relative to the electrolyte and a second set of fibers that have a different absorbency which is less than 80% relative to the electrolyte.
  • the first and second fibers are disclosed as being present in proportions such that the absorbency of the overall separator is from 75-95%.
  • a separator is disclosed which is made of a mixture of two different grades of glass fibers, one grade of chopped glass strand and a certain grade of polyethylene fibers.
  • Another prior art attempt to provide a RBSM is U.S. 4,216,280 to Kono et al.
  • the '280 patent discloses separators which comprise glass fibers entangled in the shape of a sheet without the use of a binder and have a first and second portion of glass fibers.
  • the first portion comprises glass fibers having a fiber diameter smaller than one micron; and a second portion uses glass fibers having a fiber diameter larger than 5 microns, as well as an average fiber length of at least 5 millimeters.
  • Such separators are stated to have high electrolyte retention, good mechanical strength, and good shape recovery.
  • Yet another prior art attempt to provide RBSMs is U.S. 4,367,271 to Hasegawa et al.
  • the '271 patent thus states that one prior proposal comprises a glass fiber mixed with a synthetic resin serving as a binding agent, while another type proposed involves mixing a glass fiber with a synthetic resin monofilament fiber.
  • Hasegawa et al. state that such prior approaches are inadequate because these approaches suffer a remarkable decrease in liquid absorption and that the improvement in the mechanical strength is small.
  • the '271 patent is said to provide a separator which is high in liquid absorption, high in strength, and is easy to handle.
  • Such separator materials are produced by a process which uses glass fiber substantially 1 m 2 /g or more in specific area, mixed with about 10% or less, by weight, of fibril-formed synthetic fibers which have 350 cc or less in "freeness.”
  • Such “dry out” can result from electrolyte loss, uneven cell saturation, RBSM pull away or a combination.
  • reasons for occurrence of “dry out” may include lack of appropriate resilience of the RBSM and/or formation of saturation differential from cell top to cell bottom.
  • electrolyte stratification can cause a variety of problems such as sulfation of the negative plate and uneven usage of the plate from top to bottom.
  • a further and more specific object provides separators for large VRLA cells and batteries capable of achieving enhanced resistance to electrolyte stratification over the service life.
  • Yet another specific object of this invention lies in the provision of such sealed cells and batteries having separators with a preselected separator springiness so as to provide improved performance over the service life of such cells and batteries.
  • Another object of the present invention is to provide separators for such sealed lead-acid cells and batteries exhibiting enhanced mechanical strength so as to facilitate cell and battery assembly.
  • a still further object lies in the provision of test methods useful for selecting suitable separate materials for VRLA cells and batteries.
  • the present invention is, in general, predicated on the discovery that enhanced performance over the service life of sealed lead-acid cells and batteries can be achieved by utilizing separators having preselected properties and compositions. More particularly, it has been found that the coordination of particular properties, in a particular manner, will allow separator materials that will achieve VRLA cells and batteries having improved performance over their expected service life. It has thus been found that superior separator materials are achieved when such materials combine preselected porosity and pore size characteristics and basis weights with preselected springiness and saturation and stratification characteristics.
  • FIGURE 1 is an isometric view of a lead-acid cell of the present invention, the cell jar being partially broken away to show the internal components.
  • FIGURE 1 illustrates an exemplary lead-acid cell in accordance with the present invention.
  • the cell 10 has a container or jar 12 containing a plurality of positive and negative plates 14 and 16, respectively. As illustrated, the cell contains plural positive and negative plates. Of course, the cell can utilize the necessary number of plates to provide the capacity and other electrical performance characteristics desired for the particular application.
  • the plates 14, 16 are separated by absorbent separators 18 having the characteristics preselected as will be discussed hereinafter.
  • the separator extends slightly past the electrode to prevent an inadvertent short circuit of the cell.
  • the separator may be folded around and between the plates by employing a U-fold 20, as illustrated in FIGURE 1.
  • the plates 14, 16 preferably fit snugly within the container 12, that is, the electrodes and separators should stay in the assembled condition when the container is inverted. Indeed, as is known, the cell configuration should ensure that the plates and separators maintain adequate compression and good contact so as to enhance the electrical performance of the cell.
  • the separators and plates are compressed so as to be in intimate contact with one another.
  • adequate compression can be achieved by ensuring that the thickness of the separator in the cell is compressed typically by at least about 20% to 25% or so of the uncompressed thickness.
  • the plates are connected to one another by conductive straps 22 and to external terminals, 24, 26, by conventional means.
  • the thickness of the plates will vary depending upon the application to which the cell is intended. An illustration of a useful range is from about 0.050 inch to about 0.300 inch, or even more.
  • the container is normally sealed from the atmosphere in use to provide an efficient oxygen recombination cycle as is known.
  • the container utilized should be able to withstand the pressure of the gases released during charging of the cell. Pressures inside the container may reach levels as high as, for example, 0.5-10 psig. Release venting is provided by a low pressure, self- resealing relief valve, such as for example, a valve 28. An example of such valve is illustrated in U.S. 4,401,730.
  • An electrolyte is also included within the container 12.
  • the electrolyte is absorbed within the separator in the positive and negative active material.
  • the electrolyte typically is sulfuric acid having a specific gravity in the range of, as an example, about 1.270 to about 1.340 or even more, as is considered appropriate for a particular application.
  • the size of the plates can vary depending upon the necessary electrical performance requirements for the cell. For example, conventional sizes of positive plates are rated ranging from 58 ampere-hours (AH) to 98 AH, 108 AH, 188 AH, and even greater.
  • the height of the cell can exceed 28 inches.
  • the cells for many applications require separators having thicknesses of from about 0.04 to about 0.135 inches and up to 28 inches in height, or perhaps even more.
  • the internal configuration of the sealed lead-acid cells and batteries can be varied as desired.
  • a wide variety of types of sealed lead-acid cells and batteries are known and may be used.
  • the separators need to be preselected to provide enhanced performance during the desired service life.
  • Preselecting and “preselection,” it is meant that the designated properties of the separator are determined prior to assembly of the sealed cell or battery and that the separator material utilized in the cells is included with knowledge of such properties. Such knowledge can be obtained through testing by either the separator manufacturer or user. Also, as may be appreciated, there is no need to re-test for the desired preselected properties, once reproducibility in the process parameters has been determined.
  • One aspect of the present invention provides a test technique that adequately evaluates the springiness characteristics of RBSMs so that the preselected springiness characteristics will allow enhanced performance over the service life. More particularly, a load cell test has been developed which measures the decay in the springiness characteristic over time in a continuous fashion so as to predict the ability of the RBSM to maintain compression within a cell over the service life.
  • the load cell test utilized in the present invention measures the amount of pressure exerted by the separator sample (having adequate electrolyte absorbed within the test sample to achieve 95 % saturation and an initial compression of 20%) against a load cell. A graph of the pressure versus time can be generated. Over time, the pressure exerted will level off.
  • useful separator materials should have a load cell pressure at two months of at least about 6.0, preferably at least about 6.5 or 7.0, and, even more preferably, at least about 8.0.
  • test sample is prepared by cutting a 3"x3" square.
  • the actual thickness of the test sample is determined at any three points using a TMI gauge and the BCI test procedure (BCI Spec. No. 3-006 through 9) for determining the thickness of a recombinant mat.
  • the sample is then weighed to the nearest milligram (W sep ).
  • W sep milligram
  • the basis weight, bw is determined by using the BCI procedure for recombinant mats (Method A);
  • the density, D a of the material in the compressed state (i.e., in the battery application), is determined by dividing the basis weight by the sample thickness at 20% compression;
  • the amount of acid, Wi is then added to the separator sample, and the sample is enclosed in a 0.003" polyethylene film or bag, heat sealing the edges together so the sample has no excess air and little void space.
  • Any polyethylene film or bag can be used although it is preferable to utilize a film or bag having sufficiently low water vapor transmission properties so that the loss in electrolyte over two months' testing is no more than 0.20% of the total electrolyte weight.
  • the sample is centered onto an aluminum base plate of a fixture.
  • the top to the fixture (a 6"x6"x0.5" polycarbonate slab) is placed on the test sample.
  • the load cell (LCAA-100 with an LBC-014 button, Omega) is put on top of the top plate so that the button is balanced on the top plate.
  • the base of the load cell is then tightened down until the top plate of the fixture touches a spacer machined for the sample at 80% of the sample thickness and having 0.004" for the thickness of the polyethylene.
  • the data collected is a continuous plot of the pressure sensed by the load cell button over time. While a test time of two months is the time of choice for sample evaluation, lesser times can be used, if considered appropriate.
  • the properties of the separators utilized should be preselected to have Saturation and Stratification characteristics preselected to have a variance of no more than 10% for at least one, and preferably both of these characteristics, preferably a differential of no more than about 5%, and, even more preferably, no more than about 2%. Maintaining these characteristics is necessary for any VRLA cell or battery designed to function in service in an upright condition and is particularly important for taller cells, i.e., cells requiring separators having a height in excess of 10 inches or so. To test the Saturation and Stratification characteristics, a 3"xl 1" rectangle is cut.
  • the thickness of the chosen sample piece and the weight of the sample to the nearest milligram are determined, as was the case regarding the load cell test. Similarly, as was likewise done in the load cell test, the grams of 1.31 sulfuric acid necessary to be added to achieve 95% saturation was determined utilizing the protocol as described for the load test.
  • This test fixture comprises front and back 6"x24"x0.5" polycarbonate slabs.
  • One of the slabs has 3.5" sliver/ grooves laser-cut therein every inch.
  • the slabs have equidistant 3/8" holes for the hold down mechanism, viz., nuts and bolts.
  • the separator is aligned to the bottom slit of the slitted slab. Spacers are added to the bolts, machined specifically for the thickness of the sample as previously described.
  • the other slab is then brought on top of the separator sample using the bolts for guides.
  • the top of the fixture is then tightened to the spacers using the nuts.
  • the set up is allowed to stand for two months. After the stand time, the separator sample is cut into l"x3" pieces using the slits of the fixture as a guide. Each piece, on the plastic, is sequentially numbered. Each piece is then weighed with the numbered plastic sheath intact. The specific gravity is then checked for each sample using a Reichert-Jung Refractometer, and the samples are placed in their corresponding numbered beakers (viz., 250 ml beakers). Based upon this data, the acid gravity versus the height of the cell can be determined, and this determines the stratification. To determine the respective Saturation, each plastic piece is dry wiped and then weighed.
  • the wet weight of the sample, W w can be determined by subtracting the weight of the plastic from the weight of the l"x3" separator/ sheath pieces.
  • the sample pieces are then rinsed with deionized water using a simple soaking method.
  • the pH of the baths are then monitored and changed approximately 4-5 times until the pH stays above 4.5 (or whatever is the pH of the deionized water used).
  • the samples are placed into an oven, removed from the beaker and placed in a marked aluminum weighing dish. The oven is maintained at a 120°C for 24 hours with no convection.
  • the samples are then removed from the oven and placed into a desiccator until cool.
  • the samples are then weighed to the nearest milligram, providing the dry sample weight, W d . If any flaking of the sample. occurs, this should be added to the dry weight.
  • the weight of the acid, W a , in each sample is determined by subtracting the dry weight of the separator sample, W d , from the wet weight of the separator sample, W w . Then, the amount of acid, A, in grams is calculated based upon how much the separator sample would hold if 100% saturated. This calculation utilizes K, determined as previously described, and then multiplied by the dry weight of the separator sample, W d :
  • A K x W d . This calculation is carried out for each separator piece. The saturation level of each piece of separator is then calculated by dividing the actual acid held in the sample, W a , by the 100% saturated weight, A, and multiplying by 100:
  • Percent Saturation W a /A x 100 From this data, the percent saturation versus the height of the cell can be determined. While the separator samples described in the test have a sample height of 11 inches, it should be appreciated that the height of the sample can be increased to the height required for a particular VRLA cell or battery. In that event, the Saturation and Stratification characteristics still should, preferably, be within the ranges previously described. Generally, there is not a difference in specific gravity from top to bottom of material in this testing procedure as described. This same procedure is used on separator material from tested cells, for verification, and changes in saturation as well as specific gravity are observed.
  • the mean pore size varies from about 1.0 to 2.2 microns. Further, the pore size at the maximum distribution preferably varies from about 1.0 to 2.5 microns.
  • separators wherein the maximum pore size is below 15 microns, more preferably less than about 14 microns, and even more preferably, less than about 10 microns or so Pore size distribution can be used to predict the ability of the RBSM to resist the development of saturation differentials. Mean pore sizes greater than 2.8 microns have a propensity to cause saturation differentials to form, even in cells where the separators are only 5 or 6 inches in height. It has been thus been found that separators having such preferable mean and maximum pore size distribution characteristics provide enhanced performance during service. Such enhanced performances are particularly evident with cells having a relatively high aspect and intended to be used in service in an upright position. However, such separators also may be used when the cells, in service, are intended to be used in a pancake fashion, viz., positioned in service on their side. Thus, it is also believed that these characteristics assist in providing a satisfactory oxygen recombination cycle.
  • the normalized basis weight (where the RBSM contains polymer fibers, as will be discussed hereinafter) should be at least preferably above 150, between about 170 to about 200 grams/meters 2 /millimeter.
  • basis weights can be determined by the BCI technique previously referenced.
  • the porosity of the separator according to the present invention it is necessary that the porosity be adequate to provide the appropriate size of the electrolyte reservoir. Thus, the porosity becomes a design issue; and it is preferred, accordingly, to utilize separators having a porosity of at least about 90 or 91%, up to about 93% or so.
  • a glass fiber mat which includes, based upon the overall weight of the separator, from about 5% up to perhaps 30% or so of plastic fibers, preferably no more than about 12%.
  • Such separators can be made by known and conventional processes, simply incorporating into the slurry from which the separator is made, the relative amount and type of the selected fibers. Indeed, it is believed that incorporating the selected level of plastic fibers tends to provide separators having more consistent and reproducible properties in comparison to fibers containing only glass.
  • the plastic fibers utilized in the separators of the present invention are preferably polyester fibers, more preferably, polyethylene terephthalate fibers. Suitable amounts of such polyester fibers range from about 5 to about 12%, based upon the total weight of the separator. As alternatives to the preferred polyester fibers, any other acid-stable polymers could be utilized. Suitable fibers include polyolefins such as polyethylene and polypropylene. The addition of such polymeric fibers increases the resilience of the RBSM as determined by improved load properties. However, if the polymer fiber content becomes too high (e.g., 50% or more), the load properties diminish.
  • RBSM materials fabricated with a glass/polymer matrix have superior load/springy properties. These materials, however, are more hydrophobic; and the hydrophobicity directly correlates with the percent polymer content. Because of their hydrophobic nature, these materials experience difficulty in maintaining satisfactory equal saturation levels from the top of the cell to the bottom. Controlling the mean pore size to below 1.5 microns can help, but does not solve the saturation problems.
  • Such polymer fibers contained within this RBSM matrix can be treated by any known means, if desired, to convert the surface of the polyester fibers to polar aprotic-type groups, such as SO 2 , SiO 2 and other known polar aprotic groups. Such known surface treatments involve transesterification, chemical vapor deposition, grafting and/or chemical laser treatments.
  • any means capable of modifying the fiber surface to enhance the wettability to the sulfuric acid electrolyte can be utilized.
  • Increasing the level of fine fibers in the glass/polymer material also aids in resistance of the material to saturation and stratification problems.
  • whether such surface treatment is necessary depends upon the service life requirements of the cell and the total plastic fiber content.
  • a certain degree of hydrophobic properties is desirable for the separator to aid in the initial recombination cycle when the cell is saturated to the level in excess of about 90% or so, as would occur after assembly and during formation. This is particularly important in float applications. Separators utilizing only about 5% polyester or so may require no treatment at all.
  • Pancake cell designs should not require the plastic fibers to be surface treated at all, regardless of the plastic fiber content.
  • many of the currently used RBSMs comprise a combination of coarse and fine glass fiber blends to provide a surface area for such RBSMs of about 1.2 m 2 /gm or so. It may be suitable for some applications to increase the proportion of the fine fibers up to 100%. Such increased fine fiber levels will assist in achieving the necessary preselected pore size requirements to maintain even saturation from cell top to cell bottom and retard stratification. This is important for electric vehicle (EV) or cycling applications.
  • the mean pore size for 100%) fine fiber RBSM is typically less than 1.5 microns .
  • the performance of the separators of the present invention can be enhanced by adding appropriate levels of silica. Such additions can be made either during or after formation of the separator.
  • the level of SiO 2 added ranges from about 5 to about 30, based upon weight of RBSM. It is believed that the addition of the SiO 2 may provide a "cross-linking" matrix or "glueing" action between the glass and plastic fibers.
  • the SiO 2 ions may also provide SiO 2 to preferentially dissolve to the glass fibers over time and under various temperature conditions, which preserves the strength and integrity of the glass fibers.
  • the inclusion of such silica not only enhances acid wettability, but also serves to maintain the springiness of the separator in service. Even further, it has been found that the inclusion of the silica enhances the ability of such separators to maintain saturation and prevent stratification of the electrolyte from the top of the cell to the cell bottom.
  • Fillers other than silica can be used, if desired, particularly if such fillers enhance wettability and/or maintaining saturation and/or preventing stratification and/or springiness of the resulting separator. Any such fillers should not, of course, be unduly deleterious to the desired performance of the VRLA cells.
  • coupling agents can be utilized to bond the fibers in the separators into a cohesive matrix. Suitable coupling agents should be stable in the cell environment and not be detrimental to the cell performance.
  • the stability and integrity of the RBSMs in the cell environment becomes an important issue so as to avoid, or at least minimize, long performance declines due to separator deterioration.
  • glass fibers are superior to polymer fibers as far as stability and integrity are concerned.
  • a multiple layer, dual functional, separator is used.
  • a glass separator layer is positioned adjacent the positive electrodes and a composite glass/polymer separator layer having the desired preselected properties is positioned adjacent the glass fiber layer to achieve the desired porosity, springiness and saturation and stratification characteristics, and protect the polymer/additives from oxidative degradation.
  • the respective thicknesses of each layer can be varied as desired to satisfy the necessary characteristics considered appropriate. In this regard, by way of example, it will generally be desirable for the composite separator layer to comprise the majority of the thickness, up to perhaps 70% or so of the total thickness.
  • the separator used in the VRLA cells can comprise multiple layers of the glass/polymer separators having the preselected properties, if desired.
  • the spatial configurations other than that previously described can be utilized all through the interface adjacent the separator and the positive electrode should be the region where separator stability will be most severely tested.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Cell Separators (AREA)
  • Secondary Cells (AREA)

Abstract

On améliore les caractéristiques de durée de vie d'accumulateurs et batteries au plomb scellés au moyen de séparateurs dotés de caractéristiques présélectionnées, y compris une pression de cellule de chargement d'au moins 6,0 environ à deux mois, des caractéristiques de saturation et de stratification présentant une variance ne dépassant pas 10 % environ, une taille des pores maximale inférieure à 15 micromètres environ et une taille des pores moyenne inférieure à 2,8 environ.
PCT/US1999/018499 1998-08-18 1999-08-17 Separateur pour accumulateurs ou batteries au plomb WO2000011746A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
KR1020007004150A KR20010031203A (ko) 1998-08-18 1999-08-17 납-산 전지 또는 배터리용 세퍼레이터
AU54850/99A AU5485099A (en) 1998-08-18 1999-08-17 Separator for lead-acid cells or batteries
EP99941138A EP1031170A1 (fr) 1998-08-18 1999-08-17 Separateur pour accumulateurs ou batteries au plomb
CA002306691A CA2306691A1 (fr) 1998-08-18 1999-08-17 Separateur pour accumulateurs ou batteries au plomb
JP2000566913A JP2002523880A (ja) 1998-08-18 1999-08-17 鉛−酸セパレータ、及びこのようなセパレータを使用するセル及びバッテリー

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US9696398P 1998-08-18 1998-08-18
US60/096,963 1998-08-18

Publications (2)

Publication Number Publication Date
WO2000011746A1 true WO2000011746A1 (fr) 2000-03-02
WO2000011746A8 WO2000011746A8 (fr) 2000-07-20

Family

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PCT/US1999/018499 WO2000011746A1 (fr) 1998-08-18 1999-08-17 Separateur pour accumulateurs ou batteries au plomb

Country Status (6)

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EP (1) EP1031170A1 (fr)
JP (1) JP2002523880A (fr)
KR (1) KR20010031203A (fr)
AU (1) AU5485099A (fr)
CA (1) CA2306691A1 (fr)
WO (1) WO2000011746A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100787418B1 (ko) * 2001-03-02 2007-12-21 삼성에스디아이 주식회사 이온전도성이 향상된 리튬 2차 전지 및 그 제조방법
WO2008150967A2 (fr) * 2007-06-01 2008-12-11 Daramic Llc Séparateur d'accumulateur au plomb comportant une rigidité améliorée

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7360877B2 (ja) * 2019-09-27 2023-10-13 旭化成株式会社 鉛蓄電池用セパレータ、および鉛蓄電池

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EP0121771A1 (fr) * 1983-03-16 1984-10-17 Grace GmbH Séparateur pour accumulateurs au plomb
JPS63252354A (ja) * 1987-04-08 1988-10-19 Matsushita Electric Ind Co Ltd 密閉形鉛蓄電池
EP0507090A1 (fr) * 1991-03-09 1992-10-07 Daramic, Inc. Accumulateur de plomb/d'acide sulfurique
EP0515105A2 (fr) * 1991-05-23 1992-11-25 Nippon Sheet Glass Co., Ltd. Séparateur de matériau en feuilles et batterie au plomb-acide régulée par une vanne
US5225298A (en) * 1989-02-27 1993-07-06 Yuasa Battery Co., Ltd. Sealed lead acid battery and separator for use in sealed lead acid battery
EP0680105A1 (fr) * 1994-04-06 1995-11-02 Sociedad Espanola Del Acumulador Tudor, S.A. Accumulateur électrique

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EP0121771A1 (fr) * 1983-03-16 1984-10-17 Grace GmbH Séparateur pour accumulateurs au plomb
JPS63252354A (ja) * 1987-04-08 1988-10-19 Matsushita Electric Ind Co Ltd 密閉形鉛蓄電池
US5225298A (en) * 1989-02-27 1993-07-06 Yuasa Battery Co., Ltd. Sealed lead acid battery and separator for use in sealed lead acid battery
EP0507090A1 (fr) * 1991-03-09 1992-10-07 Daramic, Inc. Accumulateur de plomb/d'acide sulfurique
EP0515105A2 (fr) * 1991-05-23 1992-11-25 Nippon Sheet Glass Co., Ltd. Séparateur de matériau en feuilles et batterie au plomb-acide régulée par une vanne
EP0680105A1 (fr) * 1994-04-06 1995-11-02 Sociedad Espanola Del Acumulador Tudor, S.A. Accumulateur électrique

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Title
PATENT ABSTRACTS OF JAPAN vol. 013, no. 068 (E - 716) 16 February 1989 (1989-02-16) *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100787418B1 (ko) * 2001-03-02 2007-12-21 삼성에스디아이 주식회사 이온전도성이 향상된 리튬 2차 전지 및 그 제조방법
WO2008150967A2 (fr) * 2007-06-01 2008-12-11 Daramic Llc Séparateur d'accumulateur au plomb comportant une rigidité améliorée
WO2008150967A3 (fr) * 2007-06-01 2009-12-30 Daramic Llc Séparateur d'accumulateur au plomb comportant une rigidité améliorée
US9190648B2 (en) 2007-06-01 2015-11-17 Daramic Llc Lead-acid battery separator having enhanced stiffness

Also Published As

Publication number Publication date
JP2002523880A (ja) 2002-07-30
KR20010031203A (ko) 2001-04-16
EP1031170A1 (fr) 2000-08-30
AU5485099A (en) 2000-03-14
WO2000011746A8 (fr) 2000-07-20
CA2306691A1 (fr) 2000-03-02

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