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EP0182852A1 - Lead battery - Google Patents

Lead battery

Info

Publication number
EP0182852A1
EP0182852A1 EP85902627A EP85902627A EP0182852A1 EP 0182852 A1 EP0182852 A1 EP 0182852A1 EP 85902627 A EP85902627 A EP 85902627A EP 85902627 A EP85902627 A EP 85902627A EP 0182852 A1 EP0182852 A1 EP 0182852A1
Authority
EP
European Patent Office
Prior art keywords
lead
electrodes
cells
battery according
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP85902627A
Other languages
German (de)
French (fr)
Inventor
Ivan Lipovetz
Peter GYÖRGYFALVAY
Oszkar Rihmer
Johann Willinger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
GYORGYFALVAY PETER
Gyorgyfalvay Peter
LIPOVETZ Ivan
RIHMER Oszkar
Original Assignee
GYORGYFALVAY PETER
Gyorgyfalvay Peter
LIPOVETZ Ivan
RIHMER Oszkar
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by GYORGYFALVAY PETER, Gyorgyfalvay Peter, LIPOVETZ Ivan, RIHMER Oszkar filed Critical GYORGYFALVAY PETER
Publication of EP0182852A1 publication Critical patent/EP0182852A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • H01M10/08—Selection of materials as electrolytes
    • H01M10/10—Immobilising of electrolyte
    • 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
    • H01M10/18—Lead-acid accumulators with bipolar 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/68—Selection of materials for use in lead-acid accumulators
    • H01M4/685—Lead alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0005—Acid electrolytes
    • 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 invention relates to a lead-acid battery which contains cells connected in series, of which the two outer cells are connected to electrical connections, and electrodes which are separated from one another by corresponding spacings in the individual cells, while liquid-impermeable partition walls are inserted between the individual cells .
  • the accumulator is known to be filled with dilute sulfuric acid at a concentration of 25 to 40%.
  • the lead-acid battery according to the invention can also be produced in a closed version, in which a specific solution which far exceeds the known specific powers (power per weight unit) can be delivered;
  • the active mass of the electrodes consisting of lead oxide and lead sulfate (lead vitriol) is known to be painted onto the grid, which is conventionally produced as a press casting, then the active mass is dried and the relatively large surface area for the desired chemical reactions is ensured .
  • the material of the carrier grid is lead hardened with ordinary alloy substances, which is less resistant to sulfuric acid as an electrolyte.
  • the lead batteries are made up of cells, the individual cells being provided with walls made of insulating material. In a cell, several adjacent electrode plates are attached side by side and alternately on an anode rail or. Cathode rail connected.
  • the batteries for motor vehicles are said to satisfy numerous, opposing demands at the same time.
  • the possibility of a large current draw when starting the vehicle and, on the other hand, an uninterrupted power supply to the electrical units of the vehicle are to be ensured.
  • the size of the charging current and the discharge current should also be taken into account. If a charging voltage or a laate voltage greater than 2.38 V is used, the water in the electrolyte disintegrates electrolytically, the voltage limit mentioned must not be exceeded for a long time during battery operation.
  • the completely closed versions i.e. those without gas outlet openings, can only be used with a relatively complicated structure and special material selection,
  • the aim of the invention is to create a lead acid battery which frees itself from the above-mentioned disadvantages and has a greater energy density than the known outer guiding forms, so that the same power can be delivered with the same absenteeism and smaller weight.
  • the invention is based on the knowledge that the thick lead grids that have been used more widely up to now can be replaced if the known one
  • Painted plate technology is replaced by another technology.
  • the task of creating a lead acid battery was solved with a constant lead acid battery, which can be planned particularly well for uniform uses, and which contains cells connected in series, of which the two external cells are connected to electrical connections, and in the individual cells from one another by corresponding Raunabatands separate electrodes arranged and liquid-tight between the cells
  • the electrodes are designed according to the invention as a layer applied from lead as a starting material by metal spraying.
  • the electrodes can preferably be surfaces formed on a lead plate, which are attached between the partition walls, the wall separating the cells made of a metal or metallic conductive material resistant to the dilute sulfuric acid, for example graphite or expediently of a thickness of at least 0.1 mm Lead plate is made. They form on this lead plate Electrodes of a single or multi-layer construction with lead base material,
  • a layer is formed in the electrode which consists of lead alloyed with barium silicide from 0.1 to 2.0, preferably from 0.6 percent by weight.
  • a network of insulating material e.g. made of washed fiberglass-free glass fiber, the edge of which projects beyond the surface of the carrier or the partition covered with the electrode.
  • the cell separating and electrically conductive wall simultaneously separates the liquids filling the neighboring cells from one another and an electrical between the one given polarity of the one cell and the other opposite polarity of the other cell Series connection secures. So these electrically conductive partitions can also be arranged horizontally, the harmful appearance of a voltage gradient should not be expected.
  • the battery can be mounted in a closed housing if a separator formed by colloidal silicic acid anhydride is used in the space between the partition walls separating the individual cells in a liquid-tight manner and contains silicon disulfide from 1.8 to 10, preferably from 2.6 percent by weight and with that Sulfuric acid as an electrolyte forms a gel-like substance, Daa silicon diaulfide disintegrates in water and favors the Chinese cells that play in the battery Reactions.
  • a separator formed by colloidal silicic acid anhydride is used in the space between the partition walls separating the individual cells in a liquid-tight manner and contains silicon disulfide from 1.8 to 10, preferably from 2.6 percent by weight and with that Sulfuric acid as an electrolyte forms a gel-like substance, Daa silicon diaulfide disintegrates in water and favors the Chinese cells that play in the battery Reactions.
  • the lead-acid battery according to the invention can be accommodated in a plastic battery box and can be operated during its entire lifespan with appropriate operation, especially without peak loads and with continuous and even use without any maintenance.
  • the energy density was based on a value of 80 to 110 Wh / kg by weight and based on volume on a value of 750 to 950 Wh / dm 3 (instead of the previous value of 48 to 110 Wh / dm 3 ). elevated.
  • the proposed lead-acid battery (acid battery) is essentially constructed according to the known principles, whereby it consists of cells connected in series, of which the two outside cells are connected to a positive pole or a negative pole.
  • a partition 1 is arranged between the adjacent cells, which is a liquid-tight plate.
  • electrodes 2 made of lead base material are applied electrolytically or by metal spraying to a corresponding carrier in the proposed lead battery.
  • An electrode 2 can e.g. on a perforated or smooth, at least 0.1 mm thick lead plate are applied, which are used in the known batteries ala cathode or as an anode
  • the thickness of the lead plate is determined by the respective stresses, inter alia by the fact that the processes that take place during the operation of the battery can cause a mechanical deformation in the material of the electrodes 2.
  • the other possibility of radically improving the characteristics of the battery of the electrodes 2 is that they are applied electrolytically or by metal spraying to both sides of the partition 1 and geniasan ensure their liquid-tight property.
  • the use of the lead plates between the partition walls in the individual cells is superfluous.
  • the partition 1 is made of an electrically conductive material which is resistant to the dilute sulfuric acid and is expediently made of graphite or lead. The thickness of such a partition 1 is also determined here by the operating conditions.
  • Each end partition 1 of the outside cells is connected to the electrical connections in the battery designed in this way.
  • the battery can therefore also be operated horizontally with horizontal partition walls 1.
  • the partition walls 1 take part in the formation of the circuit with their entire surface in every spatial position of the battery, so the formation of a harmful voltage gradient during charging and discharging can be avoided, which at least limits the possibility of gas formation.
  • the electrode 2 is suitably made up of several layers.
  • a lead layer is applied to the carrier element, for example to the partition 1, using a known technology, for example by electrolysis or metal spraying.
  • a mesh 4 and a second lead layer are applied to this layer.
  • the network 4 consists of an insulating material, while the lead layer expediently contains barium silicide from 0.1 to 2.0, preferably from 0.6 percent by weight, which, in addition to the appropriate electrical parameters, ensures the stability required during battery operation.
  • the partition 1 is to be attached together with the applied electrodes 2 in a holding frame 5 in which a liquid-tight bedding is formed.
  • the net 4 protrudes over the surface of the electrode 2 and is attached, for example, welded, to the holding frame.
  • Holding frames 5 are made of insulating material and expediently arranged in a box 6, in which the cells are formed with the aid of the partition walls 1 and form an electrical chain through the partition walls 1 and with the aid of the electrolyte.
  • a separator 3 is preferably arranged in the liquid-tight sealed cells and advantageously consists of silicon disulphide of 1.8 to 10.0, preferably 2.5% by weight, of silicic acid anhydride as the colloidal substance.
  • the separator 3 has a much greater viscosity than that of the Sulfuric acid.
  • the function of the separator 3 is to hold the electrolyte between the electrodes 2 and at the same time to ensure a space spacing so that the electrodes 2 cannot come into contact with one another in any position of the partition walls 1.
  • the gel-like substance is also particularly suitable for preventing the electrolyte from running out in the event of mechanical damage to the battery box 6.
  • the electrodes 2 are expediently designed with a multilayer structure, and the barium silicide alloys on the two sides of the network 4 are 0.5 to 0 , 7 mm thick lead layers.
  • the first charging process of the lead battery according to the invention is to be carried out in a known manner. After the battery stops gassing, the box 6 can be completely closed and the hermetically sealed battery can be put into operation.
  • the lead-acid battery according to the invention is durable thanks to its structure for the operation of everyone steady load suitable for significant loads. It can therefore be advantageous to use an integrated circuit arrangement which ensures that the current consumption remains within a given limit, depending on the number of cells in the battery. By using such a strictly limiting arrangement, the long life of the lead-acid battery according to the invention can be ensured.
  • the significant 3 to 4-fold increase in weight and 8 to 10-fold increase in volume can be mentioned become.
  • the lifespan of the battery is also increased, since the failure of the previously applied active mass and the erosion of the electrodes are eliminated.
  • a particular advantage is the reduction in lead consumption and the improvement of the conditions of manufacture.

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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)
  • Materials Engineering (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

Pile au plomb renfermant des cellules connectées en série, dont les deux cellules extérieures sont reliées à des raccords électriques, où des électrodes (2) séparées entre elles par des intervalles appropriés sont disposées dans les diverses cellules et des parois de séparation étanches aux liquides (1) intercalées entre les cellules. La caractéristique de la présente invention est que les électrodes sont formées de matériau de plomb par métallisation par projection ou se composent de couches appliquées électrolytiquement dans les cellules.Lead cell containing cells connected in series, the two outer cells of which are connected to electrical connections, where electrodes (2) separated from each other by appropriate intervals are placed in the various cells and liquid-tight separation walls ( 1) inserted between the cells. The characteristic of the present invention is that the electrodes are formed of lead material by spray metallization or consist of layers applied electrolytically in the cells.

Description

BLEIBATTERIE LEAD BATTERY
Die Erfindung bezieht sich auf eine Bleibatterie, die in Reihe geschalteten Zellen enthält, von denen die zwei aussenseitigen Zellen nit elektrischen Anschlüssen verbunden sind, und in den einzelnen Zellen voneinander durch entsprechende Raumabstände getrennte Elektroden angeordnet sind, während zwischen den einzelnen Zellen flüssigkeitsnichtdurchlässige Trennwände eingesetzt sind. Der Akkumulator ist bekannterweise mit verdünnter Schwefelsäure mit einer Konzentration von 25 bis 40 % gefüllt. Die erfindungsgemässe Bleibatterie kann auch in geschlossener Ausführung erzeugt werden, wobei eine die bekannten spezifischen Leistungen (Leistung pro Gewichteinheit) weit übertreffende spezifische Lsitung abgegeben werden kann;The invention relates to a lead-acid battery which contains cells connected in series, of which the two outer cells are connected to electrical connections, and electrodes which are separated from one another by corresponding spacings in the individual cells, while liquid-impermeable partition walls are inserted between the individual cells . The accumulator is known to be filled with dilute sulfuric acid at a concentration of 25 to 40%. The lead-acid battery according to the invention can also be produced in a closed version, in which a specific solution which far exceeds the known specific powers (power per weight unit) can be delivered;
Stand der TechnikState of the art
Im Laufe der Fertigung der Bleibatterien wird die aus Bleioxyd und Bleisulfat (Bleivitriol) bestehende aktive Masse der Elektroden auf das herkömmlich als Pressguss hergestellte Gitter bekannterweise aufgeatrichen, dann die aktive Masse wird getrocknet und damit die relative grosse Oberfläche für den Ablauf der erwünschtoa chemischen Reaktionen gesichert. Das Material des Trägergitters ist mit gewönlichen Legierungsatoffen gehärtetes Blei, das gegen Schwefelsäure als Elektrolyt weniger beständig ist. Die Bleibatterien sind aus Zellen aufgebaut, wobei, die einzelnen Zellen mit Wänden aus Isoliermaterial versehen sind. In einer Zelle sind mehrere benachbarten Elektrodenplatten nebeneinander angebracht und wechselweise an einer Anodenschiene bzw.. Katodenschiene angeschlossen. Neben einer, als eine Katode dienender und während der Formatierung der Batterie perös werden den Bleiplatte ist eine andere, während der Formatierung mit Bleidioxyd zu überziehende und als Anode dienende Bleiplatte angeordnet. Ea folgt aud dem dargestellten Aufbau, daaa die bekannten Ausführungaformen der Bleibatterien eine ziemlich grosse Menge Blei enthalten, das in den in der Batterie abspielenden chemischen Vorgängen nicht immer völlig ausgenutzt ist. Wegen der Stromabführung durch die Schienen entateht in vielen Fällen ein schädlicher Spannungsgradient. Als dessen Folge ist das Gewicht der mit dem besten Wirkungsgrad arbeitenden bekannten Bleibatterien sehr hoch. Statt dea theoretischen Grenzwertes der Energiedichte von 175 Wh/kg iat heutzutage eine Energiedichte von 38 Wh/kg knapp erreicht. Ausser dem Blei spelen darin auch die inneren Führungsschienen eine wesentliche Rolle, die wiederum ein bedeutendes Gewicht darstellen. Eine weiterer Nachteil besteht darin, dass beim starken Entladen der Batterie ein Teil der aktiven Masse aus dem Trägergitter herausfällt und die Kapazität der Batterie sich langsam abnimmt.In the course of the production of the lead acid batteries, the active mass of the electrodes consisting of lead oxide and lead sulfate (lead vitriol) is known to be painted onto the grid, which is conventionally produced as a press casting, then the active mass is dried and the relatively large surface area for the desired chemical reactions is ensured . The material of the carrier grid is lead hardened with ordinary alloy substances, which is less resistant to sulfuric acid as an electrolyte. The lead batteries are made up of cells, the individual cells being provided with walls made of insulating material. In a cell, several adjacent electrode plates are attached side by side and alternately on an anode rail or. Cathode rail connected. In addition to a lead plate which serves as a cathode and becomes perous during the formatting of the battery, there is another lead plate which is to be coated with lead dioxide during the formatting and serves as an anode. It follows from the structure shown that the known types of lead batteries contain a fairly large amount of lead, which is not always fully utilized in the chemical processes taking place in the battery. In many cases, there is a harmful voltage gradient due to the power dissipation through the rails. As a result, the weight of the known lead acid batteries working with the best efficiency is very high. Instead of the theoretical limit value of the energy density of 175 Wh / kg iat today an energy density of 38 Wh / kg just barely reached. In addition to the lead, the inner guide rails also play an important role, which in turn represent a significant weight. Another disadvantage is that when the battery is heavily discharged, part of the active mass falls out of the carrier grid and the capacity of the battery slowly decreases.
Die Batterien für Kraftfahrzeuge sollen zahlreiche, einander entgegengesetzten Forderungen gleichzeitig befriedigen. Es soll einerseits die Möglichkeit einer gropsen Stromentnahme beim Anlassen des Fahrzeuges und andererseits eine ununterbrochene Stromspeiaung der elektrischen Einheiten des Fahrzeuges, gesichert werden. Bein Ungehen nit einer Bleibatterie soll auch die Grösse dea Ladestrones und auch des Entladestromes beachtet werden. Bei der Verwendung einer Ladespannung oder einer Laatspannung grösser als 2,38 V zerfällt das in der Elektrolyt befindliche Wasser elektrolytisch, so darf die genannte Spannunsgrenze während des Betriebes der Batterie nicht langzeitig überstiegen werden. Da dieae Möglichkeit nicht eindeutig auageschlossen werden kann, und während des Betriebes sich irgendwelches Gas bildet können die völlig geschlossenen Ausführungen, also jene ohne Gasauslassöffnungen nur bei einem relative komplizierten Aufbau und spezieller Materialwahl verwendet werden,The batteries for motor vehicles are said to satisfy numerous, opposing demands at the same time. On the one hand, the possibility of a large current draw when starting the vehicle and, on the other hand, an uninterrupted power supply to the electrical units of the vehicle are to be ensured. In the event of a lead acid battery, the size of the charging current and the discharge current should also be taken into account. If a charging voltage or a laate voltage greater than 2.38 V is used, the water in the electrolyte disintegrates electrolytically, the voltage limit mentioned must not be exceeded for a long time during battery operation. There the possibility cannot be unambiguously excluded, and any gas forms during operation, the completely closed versions, i.e. those without gas outlet openings, can only be used with a relatively complicated structure and special material selection,
Darstellung der ErfindungPresentation of the invention
Ziel der Erfindung ist es, eine Bleibatterie zu schaffen, die von den obengenannten Nachteilen befreit eine grössere Energiedichte aichert ala die bekannten Auaführungsfornen, so dass die gleiche Leistung bei gleichen Abnessungen und kleineren Gewicht abgegeben werden kann. Die Erfindung beruht auf der Erkenntnis, dass die bisher weiterverbreitet verwendeten dicken Bleigitter abgelöst werden können, wenn die bekannteThe aim of the invention is to create a lead acid battery which frees itself from the above-mentioned disadvantages and has a greater energy density than the known outer guiding forms, so that the same power can be delivered with the same absenteeism and smaller weight. The invention is based on the knowledge that the thick lead grids that have been used more widely up to now can be replaced if the known one
Technologie der gestrichenen Platten nit einer anderen Technologie abgelöst wird.Painted plate technology is replaced by another technology.
Die gestellte Aufgabe, eine Bleibatterie zu schaffen wurde nit einer beständigen, für gleichnässige Benutzungen besonders gut planbaren Bleibatterie gelöat,die in Reihe geschalteten Zellen enthält, von denen die zwei aussenseitigen Zellen mit elektrischen Anachlüssen verbunden sind, und in den einzelnen Zellen voneinander durch eatsprechende Raunabatände getrennte Elektroden angeordnet und zwischen den Zellen flüssigkeitsdichteThe task of creating a lead acid battery was solved with a constant lead acid battery, which can be planned particularly well for uniform uses, and which contains cells connected in series, of which the two external cells are connected to electrical connections, and in the individual cells from one another by corresponding Raunabatands separate electrodes arranged and liquid-tight between the cells
Trennwände eingesetzt sind.Die Elektroden sind erfindungsgemäss als eine aus Blei als Ausganganaterial durch Metallapritzen aufgetragene Schicht ausgebildet. Die Elektroden können bevorzugt auf einer Bleiplatte ausgebildete Oberflächen sein, welche zwischen den Trennwänden angebracht werden, wobei die die Zellen trennende Wand aus einem gegen die verdünnte Schwefelsäure beständigen Metall oder metalliach leitenden Material, z.B. aua Grafit oder zwecknässig aus einer mindestens 0, 1 mm dicken Bleiplatte hergestellt ist. An dieser Bleiplatte bilden die Elektroden eine ein- od er nehrachichtige Konstruktion mit Bleigrundstoff,The electrodes are designed according to the invention as a layer applied from lead as a starting material by metal spraying. The electrodes can preferably be surfaces formed on a lead plate, which are attached between the partition walls, the wall separating the cells made of a metal or metallic conductive material resistant to the dilute sulfuric acid, for example graphite or expediently of a thickness of at least 0.1 mm Lead plate is made. They form on this lead plate Electrodes of a single or multi-layer construction with lead base material,
Vom Standpunkt des Betriebes der Batterie hat sich als besonders vorteilhaft bewiesen, wenn in der Elektrode eine solche Schicht ausgebildet ist, die aus mit Bariumsilizid von 0, 1 bis 2,0, bevorzugt von 0,6 Gewichtsprozent legierten Blei besteht. Zar Verbesserung der mechanischen Festigkeit und zur Begrenzung der in Laufe der elektrochemischen Vorgänge auftretenden Deformationen iat zwischen den Schichten an mindestens einer Stelle ein Netz aus Iaoliermaterial, z.B. aus gewascheoen also von Natrium befreiten Glasfaser eingebaut, dessen Rand die mit der Elektrode bedeckte Oberfläche des Trägers oder der Trennwand überragt. Es ist ersichtlich, dass in einer bevorzugten Ausführungsform der erfindungsgemässen Bbibatterie die die Zellen trennende und elektrolisch leitende Wand gleichzeitig die die benachbarten Zellen ausfüllenden Flüssigkeiten voneinander trennt und zwischen der einen Elektrode gegebener Polarität der einen Zelle und der anderen Elektrode entgegeogesetzter Polarität der anderen Zelle eine elektrische Reihenverbindung sichert. So können diese elektriach leitenden Trennwände auch horizontal angeordnet werden, wobei mit der schädlichen Erscheinung eines Spannungsgradientes nicht gerechnet werden soll.From the point of view of the operation of the battery, it has proven to be particularly advantageous if such a layer is formed in the electrode which consists of lead alloyed with barium silicide from 0.1 to 2.0, preferably from 0.6 percent by weight. To improve the mechanical strength and to limit the deformations occurring in the course of the electrochemical processes, a network of insulating material, e.g. made of washed fiberglass-free glass fiber, the edge of which projects beyond the surface of the carrier or the partition covered with the electrode. It can be seen that in a preferred embodiment of the battery according to the invention, the cell separating and electrically conductive wall simultaneously separates the liquids filling the neighboring cells from one another and an electrical between the one given polarity of the one cell and the other opposite polarity of the other cell Series connection secures. So these electrically conductive partitions can also be arranged horizontally, the harmful appearance of a voltage gradient should not be expected.
Die Batterie kann in einem geschlossenen Gehäuse angebracht werden, wenn in dem Raumabstand zwischen den die einzelnen Zellen flüsaigkeitsdicht trennenden Trennwänden ein durch kolloidales Kieselsäureanhydrid ausgebildeter Separator eingeaetzt ist, der Siliziumdisulfid von 1,8 bis 10, bevorzugt von 2,6 Gewichtaprozent enthält und mit der Schwefelsäure als Elektrolyt einen gelartigen Stoff bildet, Daa Sliziumdiaulfid zerfällt in Wasser und begünstigt die in der Batterie abspielenden chenischen Reaktionen.The battery can be mounted in a closed housing if a separator formed by colloidal silicic acid anhydride is used in the space between the partition walls separating the individual cells in a liquid-tight manner and contains silicon disulfide from 1.8 to 10, preferably from 2.6 percent by weight and with that Sulfuric acid as an electrolyte forms a gel-like substance, Daa silicon diaulfide disintegrates in water and favors the Chinese cells that play in the battery Reactions.
Die erfindungsgenässe Bleibatterie kann in einen Kunatstoff-Batteriekasten untergebracht werden und kann bei entsprechendem Betrieb, besonders ohne Spitzenbelastungen und bei anhaltender und gleichmässiger Verwendung ohne jedwelche Wartung während ihrer ganzen Lebensdauer betrieben werden. In der erfindungsgemässen Batterie iat die Energiedichte auf einen Wert von 80 bia 110 Wh/kg auf das Gewicht bezogen und auf einen Wert von 750 bis 950 Wh/dm3 auf Volumen bezogen (statt des bisherigen Wertes von 48 bis 110 Wh/dm3) erhöht.The lead-acid battery according to the invention can be accommodated in a plastic battery box and can be operated during its entire lifespan with appropriate operation, especially without peak loads and with continuous and even use without any maintenance. In the battery according to the invention, the energy density was based on a value of 80 to 110 Wh / kg by weight and based on volume on a value of 750 to 950 Wh / dm 3 (instead of the previous value of 48 to 110 Wh / dm 3 ). elevated.
Kurze Beschreibung der Zeichnung Weitere Merkmale der Erfindung werden anhand der lediglich eine Ausführungsform darstellenden Zeichnung näher erläutert, die die erfindungsgemässe Bleibatterie in Schnitt darstellt.BRIEF DESCRIPTION OF THE DRAWING Further features of the invention are explained in more detail with reference to the drawing which shows only one embodiment and which shows the lead battery according to the invention in section.
Die vorgeschlagene Bleibatterie (Säurenbatterie) ist dem Wesen nach nach den bekannten Grundsätzen aufgebaut, wobei sie aus in Reihe geschalteten Zellen besteht, von denen die zwei aussenseitigen Zellen an einen Pluspol bzw. einen Minuspol angeschlossen sind. Zwischen den benachbarten Zellen ist je eine Trennwand 1 angeordnet, die eine flüssigkeitsdichte ausgebildete Platte ist. Im Sinne der Erfindung sind in der vorgeschlagenen Bleibatterie an einem entsprechenden Trägeaienent elektrolytisch oder durch Metallspritzen aufgetragene Elektroden 2 aus Bleigrundstoff angebracht. Eine Elektrode 2 kann z.B. auf eine perforierte oder glatte, mindeatens 0, 1 mm dicke Bleiplatte aufgetragen werden, nit welchen die in den bekannten Batterien ala Kathode bzw. als Anode dienendenThe proposed lead-acid battery (acid battery) is essentially constructed according to the known principles, whereby it consists of cells connected in series, of which the two outside cells are connected to a positive pole or a negative pole. A partition 1 is arranged between the adjacent cells, which is a liquid-tight plate. For the purposes of the invention, electrodes 2 made of lead base material are applied electrolytically or by metal spraying to a corresponding carrier in the proposed lead battery. An electrode 2 can e.g. on a perforated or smooth, at least 0.1 mm thick lead plate are applied, which are used in the known batteries ala cathode or as an anode
Strukturen abgelöst werden können. Die Dicke der Bleiplatte ist durch die jeweiligen Beanspruchungen, unter anderen durch die Tatsache bestimmt, dass die während des Betriebes der Batterie abspielenden Vorgänge eine nechanische Defomation in Stoff der Elektroden 2 hervorrufen können. Die andere, die Merkmale der Batterie radikal verbessernde Möglichkeit der Herateilung der Elektroden 2 besteht darin, dass diese elektrolytisch oder durch Metallspritzen auf beide Seiten der Trennwand 1 aufgetragen werden und deren flüssigkeitsdichte Eigenschaft geneiasan sichern. In diesen Fall ist die Anwendung der Bleiplatten zwischen, den Trennwänden in den einzelnen Zellen überflüssig. Die Trennwand 1 wird in diesen Fall aus einen gegen die verdünnte Schwefelsäure beständigen und elektrisch leitenden Material, zweckaässig aus Grafit oder Blei hergestellt. Die Dicke einer solchen Trennwand 1 wird auch hier durch die Betriebsverhältnisse bestimmt. Je eine Abschluss-Trennwand 1 der aussenseitigen Zellen ist in der so ausgestalteten Batterie an den elektrischen Anschlüaaen angeschloaaen. Die Batterie kann deshalb auch liegend mit horizontalen Trennwänden 1 betrieben werden. Die Trennwände 1 nehmen in jeder räumlichen Lage der Batterie mit ihren ganzen Oberfläche in der Ausbildung des Stromkreises teil, so kann die Ausbildung eines schädlichen Spannungsgradientes während der Ladung und der Entladung vernieden werden, die die Möglichkeit der Gasbildung atark begrenzt.Structures can be replaced. The thickness of the lead plate is determined by the respective stresses, inter alia by the fact that the processes that take place during the operation of the battery can cause a mechanical deformation in the material of the electrodes 2. The other possibility of radically improving the characteristics of the battery of the electrodes 2 is that they are applied electrolytically or by metal spraying to both sides of the partition 1 and geniasan ensure their liquid-tight property. In this case, the use of the lead plates between the partition walls in the individual cells is superfluous. In this case, the partition 1 is made of an electrically conductive material which is resistant to the dilute sulfuric acid and is expediently made of graphite or lead. The thickness of such a partition 1 is also determined here by the operating conditions. Each end partition 1 of the outside cells is connected to the electrical connections in the battery designed in this way. The battery can therefore also be operated horizontally with horizontal partition walls 1. The partition walls 1 take part in the formation of the circuit with their entire surface in every spatial position of the battery, so the formation of a harmful voltage gradient during charging and discharging can be avoided, which at least limits the possibility of gas formation.
Die Elektrode 2 bestent zweckmässig aua mehreren Schichten, Auf das Trägerelement, z.B. auf die Trennwand 1 wird eine Bleischicht mit einer bekannten Technologie, z.B. durch Elektrolysis oder Metallapritzen aufgetragen. Auf diese Schicht wird ein Netz 4 und darauf eine zweite Bleischicht aufgetragen. Das Netz 4 beateht aus einem Isolierstoff, während die Bleischicht zweckmässig Bariumsilizid von 0, 1 bis 2, 0, bevorzugt von 0,6 Gewiohtsprozent enthält, das neben den entaprechenden elektrischen Parametern die während des Betriebs der Batterie notwendige Stabilität sichert. Das Netz 4, das z.B. aus gewaschenem Glasfaser oder aus Kunatstoff hergestellt werden kann, sichert die mechanische Stabilität der Trennwand 1. Die Trennwand 1 soll zusammen mit den aufgetragene Elektroden 2 in einem Halterahmen 5 angebracht werden, in dem eine flüssigkeitadichte Bettung ausgebildet ist. Das Netz 4 ragt über die Oberfläche der Elektrode 2 und ist am Halterahmen befestigt, z.B, angeschweisst. DieThe electrode 2 is suitably made up of several layers. A lead layer is applied to the carrier element, for example to the partition 1, using a known technology, for example by electrolysis or metal spraying. A mesh 4 and a second lead layer are applied to this layer. The network 4 consists of an insulating material, while the lead layer expediently contains barium silicide from 0.1 to 2.0, preferably from 0.6 percent by weight, which, in addition to the appropriate electrical parameters, ensures the stability required during battery operation. The net 4, which can be made of washed glass fiber or plastic, for example, ensures the mechanical stability of the partition 1. The partition 1 is to be attached together with the applied electrodes 2 in a holding frame 5 in which a liquid-tight bedding is formed. The net 4 protrudes over the surface of the electrode 2 and is attached, for example, welded, to the holding frame. The
Halterahmen 5 sind aus Isoliermaterial hergestellt und zweckmässig in einem Kasten 6 angeordnet, in welchem die Zellen mit Hilfe der Trennwände 1 ausgebildet sind und diese durch die Trennwände 1 und mit Hilfe des Elektrolyten eine elektrische Kette bilden.Holding frames 5 are made of insulating material and expediently arranged in a box 6, in which the cells are formed with the aid of the partition walls 1 and form an electrical chain through the partition walls 1 and with the aid of the electrolyte.
In den flüssigkeitsdicht abgeschlossenen Zellen ist bevorzugt ein Separator 3 angeordnet, der vorteilhaft aus Siliziumdisulfid von 1,8 bia 10, 0, bevorzugt von 2,5 Gewichtsprozent enthaltendem Kieselsaureanhidryd als kolloidaler Stoff besteht, Deart weist der Separator 3 eine viel grössere Viskosität als die der Schwefelsäure auf. Dje Aufgabe des Separators 3 besteht darin, den Elektrolyt zwischen den Elektroden 2 zu halten und gleichzeitig einen Raumabstand zu sichern, damit die Elektroden 2 in keiner lage der Trennwände 1 miteinander in Berührung kommen können. Dieaer gelartiger Stoff ist beaonders dazu geeignet, den Aualauf des Elektrolyten bei einer mechaniachen Beschädigung des Batteriekastens 6 zu verhindern, Die Elektroden 2 sind zweckmässig mit einer Mehrschichtenstruktur ausgeführt, und an den beiden Seiten des Netzes 4 sind die Bariumsilizid legierte mit 0, 5 bis 0,7 mm dicken Bleiachichten aufgetragen.A separator 3 is preferably arranged in the liquid-tight sealed cells and advantageously consists of silicon disulphide of 1.8 to 10.0, preferably 2.5% by weight, of silicic acid anhydride as the colloidal substance. The separator 3 has a much greater viscosity than that of the Sulfuric acid. The function of the separator 3 is to hold the electrolyte between the electrodes 2 and at the same time to ensure a space spacing so that the electrodes 2 cannot come into contact with one another in any position of the partition walls 1. The gel-like substance is also particularly suitable for preventing the electrolyte from running out in the event of mechanical damage to the battery box 6. The electrodes 2 are expediently designed with a multilayer structure, and the barium silicide alloys on the two sides of the network 4 are 0.5 to 0 , 7 mm thick lead layers.
Der erste Ladungavorgang der erfindungsgemäasen Bleibatterie soll auf bekannter Weise durchgeführt werden. Nachdem die Batterie aufhört zu gasen, kann der Kasten 6 vollständig abgeschlossen und die hermetisch verschlossene Batterie in Betrieb gesetzt werden.The first charging process of the lead battery according to the invention is to be carried out in a known manner. After the battery stops gassing, the box 6 can be completely closed and the hermetically sealed battery can be put into operation.
Die erfindungsgenässe Bleibatterie ist durch seinen Aufbau zur Bedienung von vor allen eine dauer hafte gleichmässige Beanspruchung bedeutenden Belastungen geeignet. Es kann deshalb vorteilhaft vorkommen, eine integrierte Schaltungsanordnung zu verwenden, durch welche gesichert wird, dass die Stromaufnahme von der Zahl der Zellen der Batterie abhängig binnen einer gegebenen Grenze bleibt. Durch die Verwendung einer solchen strenbegrenzenden Anordnung kann die lange Lebensdauer der erfindungsgenässen Bleibatterie gesichert werden, Unter den Verteilen der erfindungsgemässen Bleibatterie kann die bedeutende, auf das Gewicht bezogen 3 bis 4-fache und auf das Volumen bezogen 8 bis 10-fache Erhöhung der Energiedichte erwähnt werden. Auch die Lebensdauer der Batterie wird erhöht, da der Ausfall der bisher aufgestrichenen aktiven Masse und die Erosion der Elektroden wegfällt. Einen besonderen Vorteil bedeutet die Veminderung des Bleiverbrauches und die Verbesserung der Bedingungen der Herstellung. The lead-acid battery according to the invention is durable thanks to its structure for the operation of everyone steady load suitable for significant loads. It can therefore be advantageous to use an integrated circuit arrangement which ensures that the current consumption remains within a given limit, depending on the number of cells in the battery. By using such a strictly limiting arrangement, the long life of the lead-acid battery according to the invention can be ensured. Among the distributions of the lead-acid battery according to the invention, the significant 3 to 4-fold increase in weight and 8 to 10-fold increase in volume can be mentioned become. The lifespan of the battery is also increased, since the failure of the previously applied active mass and the erosion of the electrodes are eliminated. A particular advantage is the reduction in lead consumption and the improvement of the conditions of manufacture.

Claims

PATENTANSPRÜCHE: PATENT CLAIMS:
1. Bleibatterie mit in Reihe geschalteten Zellen, von denen die zwei aussenseitigen Zellen mit elektrischen Anschlüssen verbunden und in den einzelnen Zellen voneinander durch entsprechende Raumabstände getrennte Elektroden angeordnet und zwischen den Zellen flüssigkeitsdichte Trennwände eingesetzt sind, dadurch g e k e n n z e i c h n e t , dass die Elektroden (2) in den Zellen aus Bleigrundstoff durch Metallspritzen oder als elektrolytisch aufgetragene Schichte ausgebildet sind,1. Lead battery with cells connected in series, of which the two outside cells are connected to electrical connections and electrodes are separated from one another in the individual cells by appropriate spacing and liquid-tight partition walls are inserted between the cells, characterized in that the electrodes (2) in the cells are made of lead base material by metal spraying or as an electrolytically applied layer,
2. Bleibatterie nach Anspruch 1, dadurch g e k e n n z e i c h n e t , dass die Elektroden (2) in den Zellen an zwiachen den Trennwänden (l) angeordneten Bleiplatten auagebildet sind, 2. Lead battery according to claim 1, characterized in that the electrodes (2) are formed in the cells on lead plates arranged between the partition walls (l),
3. Bleibatterie nach Anapruch 1, dadurch g e k e n n z e i c h n e t , dass die Elektroden (2) an den Trennwänden (l) einander gegenüber ausgebildet sind, wobei die Trennwand aus einem gegen die verdünnte Schwefelsäure beständigen, metalliach leitenden Material hergestellte dichte Platte iat.3. Lead-acid battery according to Anapruch 1, characterized by the electrodes (2) on the partition walls (l) being formed opposite one another, the partition wall being made of a dense plate made of a metallic conductive material that is resistant to the dilute sulfuric acid.
4. Bleibatterie nach Anapruch 3, dadurch g e k e n n z e i c h n e t , dass die Trennwand (l) aus Blei oder Grafit hergeatellt ist.4. Lead acid battery according to Anapruch 3, characterized by the fact that the partition (l) is made of lead or graphite.
5. Bleibatterie nach einem der Anaprüche 1 bis 4, dadurch g e k e n n z e i c h n e t , dass die Elektroden5. Lead-acid battery according to one of claims 1 to 4, thereby ensuring that the electrodes
(2) als eine Mehrschichtkonatruktion an den Trennwänden (l) ausgebildet aind.(2) as a multilayer construction on the partitions (l).
6. Bleibatterie nach einem der Anaprüche 1 bis 5, dadurch g e k e n n n e i c h n e t , daaa mindeatens eine Elektrode (2) mindestens eine mit Bariumsilizid von 0, 1 bis 2,0 Gewichtsprozent, bevorzugt von 0,6 Gewichtsprozent legierte Schicht enthält.6. Lead acid battery according to one of Claims 1 to 5, thereby ensuring that at least one electrode (2) contains at least one layer alloyed with barium silicide from 0.1 to 2.0 percent by weight, preferably from 0.6 percent by weight.
7. Bleibatterie nach Anspruch 5 oder 6, dadurch g e k e n n z e i c h n e t , dass zwischen zwei Schichten der Elektroden (2) ein Netz (4) aus Isolier atoff angeordnet iat, welcher die von der durch Metallapritzen aufgetragenen Schicht bedeckte Oberfläche überragt .7. Lead battery according to claim 5 or 6, characterized in that between two layers of the electrodes (2) a network (4) made of insulating atoff arranged iat, which extends beyond the surface covered by the layer applied by metal spraying.
8. Bleibatterie nach einem der Anaprüche 1 bis 7, dadurch g e k e n n z e i c h n e t , dass in dem Raumabstand zwischen den Elektroden (2) ein durch kolloidalen Kieselsäureanhydrid ausgebildeter Separator (3) angebracht ist, der Siliziumdisulfid von 1,8 bia 10,0 Gewichtaprozent, bevorzugt von 2,6 Gewichtaprozent enthält. 8. Lead battery according to one of claims 1 to 7, characterized in that in the space between the electrodes (2) a separator (3) formed by colloidal silicic acid anhydride is attached, the silicon disulfide from 1.8 to 10.0 percent by weight, preferably from Contains 2.6 percent by weight.
EP85902627A 1984-06-04 1985-06-04 Lead battery Withdrawn EP0182852A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
HU215184 1984-06-04
HU842151A HU196533B (en) 1984-06-04 1984-06-04 Lead accumulator, preferably for long-lasting uniform employment

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EP0182852A1 true EP0182852A1 (en) 1986-06-04

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EP (1) EP0182852A1 (en)
HU (1) HU196533B (en)
WO (1) WO1985005738A1 (en)

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Publication number Priority date Publication date Assignee Title
FR2648277B1 (en) * 1989-06-08 1995-12-22 Europ Accumulateurs WATERPROOF LEAD BATTERY WITH BIPOLAR ELECTRODES
FR2682817A1 (en) * 1991-10-22 1993-04-23 Gorodskoi Studenchesko Molodez Method of manufacture of an electrode for a lead accumulator and lead accumulator comprising such an electrode
US5326656A (en) * 1993-06-21 1994-07-05 General Motors Corporation Bipolar battery electrode
US5344727A (en) * 1993-06-21 1994-09-06 General Motors Corporation Bipolar battery electrode
DE102008059949B4 (en) * 2008-12-02 2013-11-07 Daimler Ag Battery, method for producing a battery and use of the battery

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CH248315A (en) * 1943-06-29 1947-04-30 Asea Ab Electric accumulator.
LU59106A1 (en) * 1969-07-15 1970-01-15
DE2250187A1 (en) * 1972-10-13 1974-04-25 Varta Batterie LEAD ACCUMULATOR WITH BIPOLAR ELECTRODES
FR2380645A1 (en) * 1977-02-15 1978-09-08 Solargen Electronics ELEMENTS AND BATTERY OF CRYSTALLINE LEAD ACCUMULATORS
DE2720250C3 (en) * 1977-05-05 1980-05-22 Accumulatorenfabrik Sonnenschein Gmbh, 6470 Buedingen Separator for a lead accumulator

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HUT40536A (en) 1986-12-28
HU196533B (en) 1988-11-28

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