US3542600A - Method of filling porous electrode matrixes with active filling material - Google Patents

Method of filling porous electrode matrixes with active filling material Download PDF

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Publication number
US3542600A
US3542600A US576745A US3542600DA US3542600A US 3542600 A US3542600 A US 3542600A US 576745 A US576745 A US 576745A US 3542600D A US3542600D A US 3542600DA US 3542600 A US3542600 A US 3542600A
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filling
matrix
ultrasonic
layer
vacuum
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US576745A
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English (en)
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Reimar Pohlmann
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VARTA AG
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VARTA AG
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/14—Electrodes for lead-acid accumulators
    • H01M4/16—Processes of manufacture
    • H01M4/20—Processes of manufacture of pasted electrodes
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49002—Electrical device making
    • Y10T29/49108—Electric battery cell making

Definitions

  • the present invention relates to a method which not only simplifies and speeds .up the filling process remarkably, but permits use of a larger amount of filling material than ever before. Briefly, this is done by first laying a thin, even layer of a pasty mixture of the filling material over an ultrasonic oscillator, then placing the electrode matrix upon the pasty layer, and then covering over the matrix with the filling paste while subjecting the system to ultrasonic pressures. It becomes evident that the viscosity of the mixture within the ultrasonic field is substantially lessened because the pasty mass, While showing a remarkable separation of fluid, flows very slightly. Within the range of effect of the ultrasonic lfield, however, the dispersed substance has a tendency to sink down, as the fiuid rises. It is therefore advantageous to treat the porous matrix from the top.
  • the means for coupling the ultrasonic energy does not have a too high ultrasonic absorption
  • the consistency of the paste should not be too high because drying of the lower layer, caused by the heat from the ultrasonic energy source, should be prevented.
  • the pasty consistency of the upper mass layer covering the matrix may be substantially higher because the ultrasonic absorption does not interfere here and it is important to bring as little fluid as possible into the pores.
  • the thickness of the entire layer should preferably be so proportioned as to meet the porosity requirements of the matrix. This means, after penetration of the pasty substance, the thickness of the remaining substance should ⁇ be close to zero.
  • the filling method practiced according to this invention may be utilized for all generally known and successfully used electrode matrixes, i.e., metallic or synthetic sinter plates, metallized sinter plates, or plates of fiber material which were obtained by sintering, pressing or Patented Nov. 24, 1970 ICC other methods.
  • complete filling may not be possible as the air may, at best, pass only partly out of the pores. It is therefore of advantage to perform the treatment at least part of the time in a vacuum.
  • the vacuum is preferably developed before the ultrasonic treatment starts so that the filling material finds already vacuumized pores at the very start of the ultrasonic oscillations.
  • the increasing pressure aids the press-in effect of the ultrasonic oscillations and thereby not only achieves remarkably higher filling amounts, but also results in noticeable time-saving of the filling-process.
  • the grain-size of the active mass filling-material should be as fine as possible, at least eq-ually fine to the capillarydimensions of the porous electrode matrix. However, a large amount of fluid will still be pressed into the matrix. It is therefore desirable to replace the volume of the fluid as much as possible with active massjIn the present invention, the ultrasonic treatment is therefore continued until a temperature is reached at which at least part of the fluid vaporizes during the treatment. This results in a bakingin of the pasty mass into the internals of the matrix. The process may be additionally aided by using a vacuum. The vaporizing may be still further accelerated by choosing a fluid with a high vapor-pressure, for instance, lower alcohols, as ether or acetone. The chemical properties of the fluid should naturally match the ones of the filling material.
  • the porous electrode matrix and the pasty mass applied thereon to the ultrasonic oscillator.
  • the pressing-on should preferably be performed by a body whose oscillation resistance is Very different from that of the paste, for example, a dry wood-block, In this case, the ultrasonic oscillations do not penetrate the pressure block, but are reflected back into the treatment area and increase the effect.
  • a wood pressure block other Inaterials such as steel or copper can be used.
  • the oscillation resistance of wood is substantially lower, the oscillation resistance of the above cited metals is substantially higher than that of the pasty filling material.
  • An especially sutiable design of the pressure block is to provide it with holes, grooves and channels on its pressing side, to encourage the fiuids tendency to flow from the area of treatment'to the pressure body. If certain precautions are overlooked, the intensive ultrasonic treatment and the pressure may have the unpleasant result of tightly baking together the oscillator, the paste, the electrode matrix and the pressure block so that upon removal of the pressure block, a substantial amount of the active filling material is torn from the pores, or the electrode matrix may even be damaged. This may be prevented by taking the precaution of covering the pressing side of the block with an anti-adhesive to prevent the baking-on.
  • An especially effective prevention method is to place a thin foil of material, such as plastic, between the filling material and the pressure block.
  • the pressure block is easily lifted off the foil and the foil itself may be removed by simply pulling it off.
  • a pressure block which is penetrable by the fluid
  • a foil should be used which likewise can be penetrated by the fiuid.
  • the filled electrode matrix is taken out by sliding the plate parallel to the surface of the working ultrasonic oscillator.
  • the upper side of the electrode may be cleaned by a spring-stripper.
  • a porous electrode matrix for example, a sinter-plate of nickel or synthetic powder or a fiber plate should be filled with electro-chemically active mass, like Cd mass.
  • the mass is pulverized to microparts of 1 micron to 10 microns and mixed homogeneously with the respective fluid until a paste having a consistency of ready-to-spread soft butter is formed.
  • the electrode matrix has a thickness of about 2 mm.
  • the applied layer on the ultrasonic oscillators should not be thicker than 2 to 3 mm.
  • the ultrasonic oscillator should be well cooled, for the content of fiuid in the mass and therefore the consistency of the lower layer should not alter after the application of the paste.
  • the matrix is layed on the layer and covered with a 3 to 4 mm. layer of paste. Subsequently this upper layer is covered with a perforated thin synthetic foil, the pressure body put on, and the air eventually removed by a vacuum pump. After reaching the vacuum limit, the pressure body will be pressed on by about 0.15 kp./cm.2 and the ultrasonic oscillator is switched on. Shortly after turning on the oscillator, the vacuum is gradually decreased until a atmospheric pressure is reached. The whole filling process takes about 10 minutes Without application of a vacuum, and 5 minutes with application of the vacuum. After the filling process is completed, which, for example, may be controlled by the extent to which particles flow off With the fluid, the pressure body is lifted up and the synthetic foil is removed.
  • the ultrasonic oscillator now carries the pasty active mass, in which the electrode matrix is embedded, filled with very dry mass. This cake itself is intimately connected with the ultrasonic oscillator.
  • the filled electrode matrix is picked up by a gripping device and slid along parallel to the oscillator surface after the ultrasonic oscillator has been put into operation again, and at the same time the layer on top of the matrix will be removed by a scraper.
  • the process of removal is now possible, as the frictional force between the tightly baked together substances decreases in the order of magnitude during the start of the ultrasonics and the filled matrix slides relatively easy on the oscillator during the ultrasonic oscillation, even if previously tightly baked together with the oscillator. After a finishing drying, the electrodes are ready to be assembled.
  • the accompanying drawings show in schematic form the operation of equipment designed for filling porous electrode matrixes with active materials wherein:
  • FIG. 1 shows the overall basic construction of the equipment
  • FIG. 2 illustrates the steps of the filling process
  • FIG. 3 shows the filling method utilizing a vacuum.
  • a stable table 1 contains a water tank 2, with the ultrasonic oscillators 3 immersed. These may be welded to a carrier plate 4 and surrounded by cooling water 5, which fiows in through feeder pipe 6 and out through exit pipe 7.
  • the oscillators are started by the high frequency input line 8 at a frequency which may, for example, range between 10 and 60 kilocycles.
  • the car- Iier plate 4 is first covered by a layer of active mass 9 which is as near as possible to uniform thickness. Over the bottom layer 9 is the porous electrode matrix 10, which is covered over with a thicker layer 11 of active mass.
  • a thin synthetic foil 12, with perforations 22, is laid between layer 11 and a pressure block 13.
  • Pressure block 13 has grooves 21 on its bottom surface to allow the fluid to drain off easier.
  • FIGS. 2a and 2b illustrate a manner of charging the equipment and FIG. 2c illustrates a manner of removing the filled electrode matrix.
  • a ⁇ V pipe or tube 14 is installed above the filling space and is moved by a sliding device which is arranged vertically to the tube axis and slides over the filling space.
  • the tube has slits, holes and nozzles, through which the active mass may be fed by a pump (not shown).
  • the carrier plate 4 has a free, bright reflection area for the ultrasonic oscillators 3.
  • the paste 16 is applied through tube 14 is spread uniformly by a solid lug 17, whose inclination may be set by an adjustable arresting device 18.
  • the tube 14 is moved in the direction of arrow 40, lug 17 is pushed against by arresting device 18 and provides a layer 9 of uniform thickness on the oscillator surface. After this is performed, the tube 14 is located at the right side of the filling space. Next the porous electrode matrix 10 is laid upon the layer 9 and the filling tube 14 slides from right to left while feeding paste in the manner illustrated in FIG. 2b. The lug 17 is positioned by a second adjustable arresting device 18 which is suitably adjusted to obtain the desired thickness of layer 11 over the electrode matrix. In the final state, the filling tube is again at the left side of the filling space, such as shown in FIG. 2c, and whereby some of the surplus paste may be slid over the edge of the filling space into the drip channel 19 (FIG. l) by lug 17 and may then fiow through the pump 20 back into the supply container.
  • arresting device 18 provides a layer 9 of uniform thickness on the oscillator surface.
  • the perforated foil 12 is applied to the top of layer 11 and the pressure block 13 is pushed down by hydraulic means or a spring tension device or something similar and the ultrasonic oscillator is switched on.
  • the active filling material is substantially liquefied and penetrates through the pores of the electrode matrix.
  • the effect shows mainly a transfer of filling material from the bottom to the top, resulting in a separation of fiuid on top of the layer.
  • the thickness of the top layer is chosen somewhat greater than the lower layer and the pressure body 13 is provided with drain channels 21 to collect the fiuid which passes through the perforation 22 in the foil 12.
  • the perforations 22 should be large enough to allow the fluid to pass through yet small enough so that the smallest particles in the pasty filling material are unable to pass through.
  • the duration of ultrasonic treatment depends upon the consistency and the like of pasty mass chosen, and may last anywhere from about 20 seconds to 15 minutes.
  • the pressure body 13 is lifted up and the foil 12 pulled off.
  • the layers are now substantially shrunken, forming a tightly baked cake containing in its inside the filled electrode matrix.
  • a third arresting device 18 which may be an altered device 18 of FIG. 2a, adjusts lug 17 to a vertical position so that it is just over the left edge of oscillator plate 4.
  • a locking device 23 on the right side of the filling space is raised against the force of spring 24, until the bottom edge 41 reaches the upper surface of the electrode matrix 10.
  • the ultrasonics are switched on again and the lug 17 and tube 14 are moved from left to right again.
  • the adhesion between the oscillator and the electrode matrix is substantially lessened, so a speedy pull-out of the matrix 10 is now possible.
  • the remainder of the upper layer 11 is also removed by the bottom edge of the locking device 23. The surplus amount of the mass drips into 25 and may be fed back to the supply container.
  • FIG. 3 illustrates schematically the manner of working using a vacuum, which may be preferred. Since the basic construction and functions are the same asin FIGS. 1 and 2, similar parts are numbered the same as in FIGS. 1 and 2.
  • the filling process is performed under the vacuum bell jar 26, which is raised and lowered by a roller conveyor 27, supported on a pillar 28 which moves by means of counter-weight 29. Before the vacuum bell jar 26 is lowered, the filling space is loaded. Then the vacuum bell jar 26 is pulled down by grasping puller 30, and pressed tightly on its rubber gaskets 31 to plate 4. By applying a vacuum in the pipe line 32 a powerful suction strength is created.
  • the pressure cylinder 33 is fed through inlet 34 with oil or air pressure which forces piston 35 down on the pressure block 24 to the desired pressure which may be controlled by gauge 36.
  • the ultrasonics are switched on and after about to 10 seconds treatment time, the vacuum line is disconnected by valve 37 and the outside air supply switched on to disrupt the vacuum as read off gauge 38.
  • the increasing pressure during the ultrasonic oscillation accelerates the transfer of the pasty mass quite decidedly. Not only is a greater filling weight obtained, but also the filling time is shortened. It is advisable to have the vacuum-bell jar locked in its suction position by locks, not shown, otherwise the pressure in cylinder 33 coupled with elimination of the vacuum within the bell jar 26 may result in the counterweight 29 lifting the bell oi the plate.
  • a method of lling porous electrode matrixes such as sinter plates, with active material for the use in batteries and the like, comprising the steps of: applying a pasty illing material in a thin even layer over an ultrasonic oscillator, laying the electrode matrix on the thin layer, covering over the matrix with .another layer of filling paste and then treating the entire combination with ultrasonic energy While under pressure.

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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)
  • Battery Electrode And Active Subsutance (AREA)
US576745A 1965-09-25 1966-09-01 Method of filling porous electrode matrixes with active filling material Expired - Lifetime US3542600A (en)

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DE (1) DE1287663B (enrdf_load_stackoverflow)
FR (1) FR1501850A (enrdf_load_stackoverflow)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3859135A (en) * 1967-02-17 1975-01-07 Lucas Industries Ltd Method of filling a battery plate grids with non-flowable battery paste
US3894886A (en) * 1972-04-17 1975-07-15 Gates Rubber Co Apparatus for pasting battery plates
US3926671A (en) * 1973-06-07 1975-12-16 Battelle Memorial Institute Method of manufacturing positive nickel hydroxide electrodes
US4020882A (en) * 1975-10-20 1977-05-03 Chloride Group Limited Manufacture of battery plates
US4037630A (en) * 1974-10-18 1977-07-26 Chloride Group Limited Manufacture of battery plates
US6089147A (en) * 1996-01-31 2000-07-18 Saitec S.R.L. Process for pressing materials

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2062344B (en) 1979-10-02 1983-06-08 Lucas Industries Ltd Lead-acid battery plates
DE3152032C1 (de) * 1981-12-31 1983-02-03 Rheinisch-Westfälisches Elektrizitätswerk AG, 4300 Essen Verfahren und Vorrichtung zum Einbringen einer Aktivmassemischung in ein Batterieelektrodengitter
DE3913061A1 (de) * 1988-05-11 1989-11-23 Deutsche Automobilgesellsch Verfahren zum vibrationsfuellen von schaum- oder faserstrukturelektrodengeruesten fuer galvanische zellen und aktivmassenpaste dazu
DE3816232C1 (enrdf_load_stackoverflow) * 1988-05-11 1989-07-20 Deutsche Automobilgesellschaft Mbh, 3000 Hannover, De
DE3817827C1 (enrdf_load_stackoverflow) * 1988-05-26 1989-11-09 Deutsche Automobilgesellschaft Mbh, 3000 Hannover, De
DE3822209C1 (enrdf_load_stackoverflow) * 1988-07-01 1989-11-02 Deutsche Automobilgesellschaft Mbh, 3000 Hannover, De
DE3822197C1 (enrdf_load_stackoverflow) * 1988-07-01 1989-08-31 Deutsche Automobilgesellschaft Mbh, 7000 Stuttgart, De

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1197737A (en) * 1914-07-01 1916-09-12 Gould Coupler Co Method of applying active material to secondary-battery plates.
US2896922A (en) * 1954-11-15 1959-07-28 Lehfeldt & Company G M B H Dr Ultrasonic means for changing the homogeneity of mixtures
DE1210417B (de) * 1963-08-12 1966-02-10 Dr Reimar Pohlman Verfahren, disperse Stoffe in poroese Koerper einzulagern
US3276975A (en) * 1964-12-11 1966-10-04 Catalyst Research Corp Silver oxide electrodes
US3282732A (en) * 1963-11-01 1966-11-01 Charles J Bradley Method of making a silver oxide electrode
US3336423A (en) * 1964-12-31 1967-08-15 Exxon Research Engineering Co Method of forming a catalytic electrode

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1197737A (en) * 1914-07-01 1916-09-12 Gould Coupler Co Method of applying active material to secondary-battery plates.
US2896922A (en) * 1954-11-15 1959-07-28 Lehfeldt & Company G M B H Dr Ultrasonic means for changing the homogeneity of mixtures
DE1210417B (de) * 1963-08-12 1966-02-10 Dr Reimar Pohlman Verfahren, disperse Stoffe in poroese Koerper einzulagern
US3282732A (en) * 1963-11-01 1966-11-01 Charles J Bradley Method of making a silver oxide electrode
US3276975A (en) * 1964-12-11 1966-10-04 Catalyst Research Corp Silver oxide electrodes
US3336423A (en) * 1964-12-31 1967-08-15 Exxon Research Engineering Co Method of forming a catalytic electrode

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3859135A (en) * 1967-02-17 1975-01-07 Lucas Industries Ltd Method of filling a battery plate grids with non-flowable battery paste
US3894886A (en) * 1972-04-17 1975-07-15 Gates Rubber Co Apparatus for pasting battery plates
US3926671A (en) * 1973-06-07 1975-12-16 Battelle Memorial Institute Method of manufacturing positive nickel hydroxide electrodes
US4037630A (en) * 1974-10-18 1977-07-26 Chloride Group Limited Manufacture of battery plates
US4020882A (en) * 1975-10-20 1977-05-03 Chloride Group Limited Manufacture of battery plates
US6089147A (en) * 1996-01-31 2000-07-18 Saitec S.R.L. Process for pressing materials

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DE1287663B (enrdf_load_stackoverflow) 1969-01-23
FR1501850A (fr) 1967-11-18

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