WO1981001075A1 - Electric storage batteries - Google Patents
Electric storage batteries Download PDFInfo
- Publication number
- WO1981001075A1 WO1981001075A1 PCT/GB1980/000157 GB8000157W WO8101075A1 WO 1981001075 A1 WO1981001075 A1 WO 1981001075A1 GB 8000157 W GB8000157 W GB 8000157W WO 8101075 A1 WO8101075 A1 WO 8101075A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- battery
- electrolyte
- intercell
- cell
- separators
- Prior art date
Links
Classifications
-
- 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
- H01M10/34—Gastight accumulators
- H01M10/342—Gastight lead accumulators
-
- 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
- H01M10/04—Construction or manufacture in general
- H01M10/0413—Large-sized flat cells or batteries for motive or stationary systems with plate-like 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
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/528—Fixed electrical connections, i.e. not intended for disconnection
-
- 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
- the present invention relates to electric storage batteries and in particular, though not exclusively, to lead acid storage batteries, and is particularly concerned with such batteries of so called “sealed” or “recombinant” type in which the amount of electrolyte present is restricted so that there is substantially no free unahsorbed electrolyte in the cells, and the gases evolved during operation or charging are induced to recombine within the battery.
- an electric storage battery has a compartment containing two cells separated from one another by an intercell partition, each cell comprising at least one positive electrode and at least one negative electrode separated from each other by separators of absorbent fibrous material and containing substantially no free unabsorbed electrolyte, the positive plates of one cell being connected to the negative plates of the other cell by an intercell connector which passes over or through the intercell partition and is not sealed thereto, in which the intercell connector is provided with an electrolyte creepage barrier.
- the electrodes and separators of each cell are within a respective plastics bag, the material of the plastics bags constituting the intercell partition.
- such an intercell partition is not sealed to the battery lid and the intercell connector merely passes over the intercell partition and is not sealed to it.
- the ba ttery's performance is not significantly impaired because intercell ionic leakage is not a serious problem in recombinant reduced electrolyte batteries.
- an electrolyte creepage barrier above the intercell partition ensures that although- wieking of electrolyte may occur along the plate straps, the electrolyte path is interrupted by the electrolyte creepage barrier so that ionic leakage currents can not pass from one cell to the other.
- the electrolyte creepage barrier may take many forms and may even comprise a non-corro ⁇ ible metallic sheath extending around and sealed to the intercell connector.
- the creepage barrier comprises a ring of plastics material moulded around the intercell connector. Such a ring may be applied by means of a four-part mould, and it will be appreciated that it is important that the ring of plastics material be substantially sealed to the intercell connector so as to prevent electrolyte wieking through a gap between the intercell connector and the creepage barrier.
- the creepage barrier comprises a film of organic material extending around the intercell connector.
- Such a film may be applied by inverting the battery after the plate straps have been formed and dipping them and the intercell connector into a bath of organic liquid such as epoxy resin or a laquer so as to leave them coated with the material which subsequently hardens.
- the creepage barriers may be applied by any convenient means, such as with a four-part mould when the plate strap is in position, or by moulding it around preformed plate straps which are subsequently connected to the plate lugs.
- the creepage barriers form an electrolyte-tight seal with the intercell connectors, but it will be appreciated that their external shape may be varied at will.
- the battery is inverted immediately after form ation of the plate straps and the latter are dipped whilst still hot into a fluidised bed of epoxy resin powder incorporating a curing agent.
- the epoxy dust sticks to the hot surface of the plate straps and cures to form an impervious layer but does not stick to the other components of the battery which, are cold.
- the cells contain essentially no free unabsorbed electrolyte, and in the most preferred condition of the cells the amount of electrolyte is not sufficient to saturate the pores in the electrodes and in the separators.
- the electrolyte absorption ratio of the separator material is preferably greater than 100%
- Electrolyte absorption ratio is the. ratio, as a percentage, of the volume of electrolyte absorbed by the wetted portion of the separator material to the dry volume of that portion of the separator material which is wetted, wh.en a strip of the dry separator material is suspended vertically above a body of aqueous sulphuric acid electrolyte of 1.270 SG containing 0.01% weight sodium lauryl sulphonate with 1 cm of the lower end of the strip immersed in the electrolyte, after a steady state wicking condition has been reached at 20oC at a relative humidity of less than 50%.
- the thickness measurement for the electrolyte absorption ratio measurement is carried out with a micrometer at a loading of 10 kilopascals (1.45 psil and a foot area of 200 square millimetres Cin accordance with the method of British. Standard Specification No. 32.89.).
- the separator material should have a wicking heigh.t of at least 5 cms on the above test namely that the electrolyte should have, risen to a height of at least 5 cms above the surface of the electrolyte into which the strip of separator material dips when the steady state condition has been reached.
- fibrous blotting paper like materials made from fibres having diameters in the range 0.01 microns, or less, up to 10 microns, the average of the diameters of the fibres being less than 10 microns and nreferably less than 5 microns
- the weight to fibre density ratio namely the ratio of the weight of the fibrous material in grams/square metre to the density in grams/cubic centimetre of the material from which the individual fibres are made preferably being at least 20 preferably 30 and especially 50.
- This combination of properties gives a material which is highly resistant to "treeing through”, namely growth of lead dendrites from the positive electrode of a lead acid battery to the negative electrode producing short circuits, whilst at the same time, even when containing large amounts of absorbed electrolyte, still providing a substantial degree of gas transmission capability.
- the amount of electrolyte added is typically inthe range 7 to 12 mis of sulphuric acid of 1.270 SG per cell in the discharged state of the cell, per Amphere hour of capacity of the cell.
- Recombinant lead acid batteries operate under superatmospheric pressure e.g. from 1.1 bars upwards and due to the restricted amount of electrolyte, the high electrolyte absorption ratio of the separator, and there being at least as much negative active material capacity as positive active material capacity and the higher electrochemical efficiency of the negative electrode, the cell operates under the so-called "oxygen cycle" in which oxygen during charging or overcharging at the positive is transported, it is believed, through the gas phase in the separator to the surface of the negative which is damp with sulphuric acid and there recomhines with the lead to form lead oxide which is converted to lead sulphate by the sulphuric acid. Loss of water is thus avoided as is excess gas pressure inside the cell. If the charging conditions generate oxygen at a faster rate than it can be transported to the negative and react thereat, then the excess oxygen is vented from the cell.
- the amount of electrolyte added is not highly critical since it is observed that if a slight excess of electrolyte is added above that required to saturate the porosity of the cell components the recombination mechanism is suppressed and electrolyte is lost by electrolysis until the electrolyte volume has reached the correct amount for the cell in question, i.e. the cell porosity has reached the correct degre.e of unsaturation, when the recombination mechanism comes into operation again and a steady state recombination condition related to the rate of charging which is used is established.
- the electrodes may be spirally wound or prismatic, e.g. of cast, cast and rolled, rolled and punched or expanded rectilinear form.
- the prismatic electrodes may be folded and interleaved or arranged in a zig-zag interleaved relationship..
- Conventional grid alloys may be used to make the electrodes but for the folded or wound embodiments, softer materials such as pure lead or lead/calcium alloys e.g. with up to 0.1% calcium and optionally up to 1.0% tin are preferred.
- Gas venting means are preferably provided in the form of a non-return valve so that air cannot obtain access to the interior of the battery although gas generated therein can escape to atmosphere.
- the intercell partition must resist degradation by the electrolyte.
- it may be polyethylene or polypropylene or polyvinyl chloride film for a lead acid battery, and may have a thickness of less than 0,010 inches.
- Figure 1 is a perspec tive view of a recombinant multicell battery having flat plates in accordance with. the present invention with one corner cut away;
- Figure 2 is a electron scanning photomicrograph of a preferred separator material at 1000 fold magnification
- Figure 3 is a view similar to Figure 2 at 4000 fold magnification.
- the battery has a container 10 of plastics material such as polypropylene containing six cell packs 1*4.
- a cell pack is made up by assembling a stack of positive and negative plates, each of which has a plate lug, interleaved with compressible absorbent microfine glass material which will be described in more detail below.
- the stack is then inserted into a plastics bag 18, of for instance polypropylene which is seamed at 20.
- the plastics bag extends up above the plates and separators, but not as far as the tops of the plate lugs.
- the container has no fixed intercell partions and the plastics bags 18 serve the function of the partitions. As mentioned above the' plastics bags extend above the tops of the separators and plates and this is important since it ensures that the separator material in adjacent cells cannot come into contact.
- each cell pack is connected together by respective plate straps 22 which are fused to the plate lugs in any conventional manner.
- the plate straps 22 are of rectangular section, and at the portion where they form intercell connectors, that is to say where they pass over the intercell partitions, they are each provided with an electrolyte creepage barrier 24 extending about 1 cm along the plate straps/intercell connectors and about 5 mm thick, their external shape corresponding to that of the plate straps.
- a reduced amount of electrolyte is added to each cell, either prior to sealing, e.g. hot plate welding a lid to the container or after such sealing, e.g. by injecting through holes in the lid. It is not critical if the bags should extend slightly above the plate lugs, since the flexible plastics material will simply be depressed by the mould in which the plate straps are formed, or by the plate straps themselves.
- the electrode supports are cast prismatic grids made from a lead, 0.07% calcium, 0.7% tin alloy. The grids are 1.2 mms thick and are rigid and self supporting and resist deformation even under load. They have good creep resistance.
- the separators are highly absorbent blotting paperlike short staple fibre glass matting about 1 mm thick, there being fibres ⁇ l as thin as 0.2 microns and fibres 60 as thick as 2 microns in diameter, the average of the diameters of the fibres being about 0.5 microns.
- Figures 2 and 3 show this material at different magnifications, Figure 2 at 1000 fold and Figure 3 at 4000 fold.
- the material whilst highly absorbent still has a very large amount of open space between the individual fibres.
- the material when tested for its wicking and electrolyte absorption capabilities as. described above absorbs electrolyte so that the liquid has wicked .up to a height of 20 cms after 2 hours and this is th.e steady state condition. This 20 cms of material absorbs 113% of its own dry volume of electrolyte, and this is its electrolyte absorption ratio.
- the separator material weighs 200 grams/square metre and has a porosity of 90-9.5% as measured by mercury intrusion penetrometry. The density of the glass from which the fibres of the separator are made is 2.6.9 g/cc; the weight to fibre density is thus 74.
- the arrangement shown in Figure 1 may be assemble by forming plate packs of interleaved pasted plates and separators and partitions in a jig and then inserting the complete assembly into the container, or the cell packs may be inserted sequentially into the container and electrolyte then added to the cells.
- the battery terminals are then connected to or formed on the plate straps and the lid sealed to the container
- the plastics bags extend up above the intercell connectors which pass through, open topped slots formed in the material of the bag.
- the electrolyte creepage barrier is secured to the lid of the battery. This may be achieved by adhesive, but is preferably achieved by hot welding at the same time as the lid is welded to the case, and. gives the cell packs additional s tability which may be required for certain application due to the absence of fixed intercell partitions.
- the battery is inverted immediately after formatio of the plate straps and the latter are. dipped whilst still hot into a fluidised bed of epoxy resin powder incorporating a curing agent.
- the epoxy dust sticks to the hot surface of the plate straps and cures to form a impervious layer but does not stick, to the other components of the battery which are cold.
- the imperyio layer of epoxy resin acts as the electrolyte creepage barrier .
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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)
- Secondary Cells (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU63380/80A AU530843B2 (en) | 1979-10-08 | 1980-10-08 | Electric storage batteries |
DE803049934T DE3049934A1 (en) | 1979-10-08 | 1980-10-08 | ELECTRIC STORAGE BATTERIES |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB7934793 | 1979-10-08 | ||
GB7934793 | 1979-10-08 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1981001075A1 true WO1981001075A1 (en) | 1981-04-16 |
Family
ID=10508349
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB1980/000157 WO1981001075A1 (en) | 1979-10-08 | 1980-10-08 | Electric storage batteries |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP0037817B1 (en) |
WO (1) | WO1981001075A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0055888A2 (en) * | 1980-12-29 | 1982-07-14 | Gates Energy Products Inc. | Multicell recombining lead-acid battery |
EP0176597A1 (en) * | 1984-03-29 | 1986-04-09 | Matsushita Electric Industrial Co., Ltd. | Sealed battery |
EP0207742A2 (en) * | 1985-06-27 | 1987-01-07 | Chloride Group Public Limited Company | Multicell recombination electric storage batteries |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SE513609C2 (en) | 1999-05-12 | 2000-10-09 | Ericsson Telefon Ab L M | Procedure in a telecommunications system |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1246427A (en) * | 1958-12-19 | 1960-11-18 | Accumulatoren Fabrik Ag | Gas-tight shut-off electric accumulator with acid electrolyte |
US3311509A (en) * | 1964-05-28 | 1967-03-28 | Globe Union Inc | Method of sealing intercell battery connections |
US3350237A (en) * | 1962-06-12 | 1967-10-31 | Lucas Industries Ltd | Method of making electric storage batteries |
DE1671875A1 (en) * | 1964-07-18 | 1971-12-23 | Hermann Papst | accumulator |
DE2333788A1 (en) * | 1972-06-28 | 1974-01-17 | Tudor Ab | CORROSION-PROTECTED LEAD-THROUGH FOR ELECTRIC ACCUMULATORS |
FR2229144A1 (en) * | 1973-05-10 | 1974-12-06 | Fulmen | |
US3862861A (en) * | 1970-08-03 | 1975-01-28 | Gates Rubber Co | Maintenance-free type lead acid |
FR2275894A1 (en) * | 1974-06-20 | 1976-01-16 | Accumulateurs Fixes | Accumulator bank interconnection - connections made through cell walls, connector acting also as wall seal and cell clamp |
FR2312122A1 (en) * | 1975-05-21 | 1976-12-17 | Chloride Group Ltd | ALKALINE TYPE ACCUMULATORS |
FR2339257A1 (en) * | 1976-01-20 | 1977-08-19 | Hoppecke Zoellner Sohn Accu | LOW WEIGHT LEAD ACCUMULATOR |
US4051304A (en) * | 1975-02-21 | 1977-09-27 | Chloride Group Limited | Electric batteries |
GB2041632A (en) * | 1979-01-17 | 1980-09-10 | Lucas Industries Ltd | Electric storage batteries |
-
1980
- 1980-10-08 WO PCT/GB1980/000157 patent/WO1981001075A1/en active IP Right Grant
-
1981
- 1981-04-21 EP EP80901853A patent/EP0037817B1/en not_active Expired
Patent Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1246427A (en) * | 1958-12-19 | 1960-11-18 | Accumulatoren Fabrik Ag | Gas-tight shut-off electric accumulator with acid electrolyte |
US3350237A (en) * | 1962-06-12 | 1967-10-31 | Lucas Industries Ltd | Method of making electric storage batteries |
US3311509A (en) * | 1964-05-28 | 1967-03-28 | Globe Union Inc | Method of sealing intercell battery connections |
DE1671875A1 (en) * | 1964-07-18 | 1971-12-23 | Hermann Papst | accumulator |
US3862861A (en) * | 1970-08-03 | 1975-01-28 | Gates Rubber Co | Maintenance-free type lead acid |
US3862861B1 (en) * | 1970-08-03 | 1987-04-07 | ||
DE2333788A1 (en) * | 1972-06-28 | 1974-01-17 | Tudor Ab | CORROSION-PROTECTED LEAD-THROUGH FOR ELECTRIC ACCUMULATORS |
FR2229144A1 (en) * | 1973-05-10 | 1974-12-06 | Fulmen | |
FR2275894A1 (en) * | 1974-06-20 | 1976-01-16 | Accumulateurs Fixes | Accumulator bank interconnection - connections made through cell walls, connector acting also as wall seal and cell clamp |
US4051304A (en) * | 1975-02-21 | 1977-09-27 | Chloride Group Limited | Electric batteries |
FR2312122A1 (en) * | 1975-05-21 | 1976-12-17 | Chloride Group Ltd | ALKALINE TYPE ACCUMULATORS |
FR2339257A1 (en) * | 1976-01-20 | 1977-08-19 | Hoppecke Zoellner Sohn Accu | LOW WEIGHT LEAD ACCUMULATOR |
GB2041632A (en) * | 1979-01-17 | 1980-09-10 | Lucas Industries Ltd | Electric storage batteries |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0055888A2 (en) * | 1980-12-29 | 1982-07-14 | Gates Energy Products Inc. | Multicell recombining lead-acid battery |
EP0055888A3 (en) * | 1980-12-29 | 1982-08-11 | The Gates Rubber Company | Multicell recombining lead-acid battery |
EP0176597A1 (en) * | 1984-03-29 | 1986-04-09 | Matsushita Electric Industrial Co., Ltd. | Sealed battery |
EP0176597A4 (en) * | 1984-03-29 | 1988-01-07 | Matsushita Electric Ind Co Ltd | Sealed battery. |
EP0207742A2 (en) * | 1985-06-27 | 1987-01-07 | Chloride Group Public Limited Company | Multicell recombination electric storage batteries |
EP0207742A3 (en) * | 1985-06-27 | 1987-04-01 | Chloride Group Public Limited Company | Multicell recombination electric storage batteries |
Also Published As
Publication number | Publication date |
---|---|
EP0037817A1 (en) | 1981-10-21 |
EP0037817B1 (en) | 1984-07-04 |
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