RU2584699C1 - Lead-acid battery - Google Patents

Abstract

FIELD: storage batteries.

SUBSTANCE: invention relates to lead-acid battery containing housing closed in upper part by cover and divided into compartments to accommodate batteries connected in series with help of inter-element connections, each accumulator consists of a unit of unlike electrodes separated by separators and electrolyte, electrodes consist of current taps and active mass, current leads of positive electrodes are made of lead-tin-calcium alloy with aluminium and silver additives, active mass of positive and negative electrodes is coated with fixing layers of porous acid-resistant material, is characterised by that alloy of positive current leads additionally contains bismuth Bi 150÷500 ppm, other components are contained in an amount of, wt%: Sn 2.0±0.1 %; Ca 0.04±0.005 %; Al 0.005±0.001 %; Ag 0.007÷0.04 %, lead - balance, and alloy bridges of inter-element connections (MES) contains main components: Sn 3±0.1 %; Sb 1.0±0.1 %; As 0.055±0.015 %; Se 0.008±0.001 %; Cu 0.013±0.002 %; lead - balance. Active mass of positive and negative electrodes fully covers on both sides units of arrays, pasting web is made of a mixture of microfibres of glass and synthetic fibres, with specific surface area not less than 1.5-2.0 m²/g, dividing separators represent envelopes of high-molecular polyethylene with arranged thereon two-sided vertical ribs or laminated glass envelope, inner side facing positive electrode.

EFFECT: longer service life and reliability of accumulator.

7 cl, 1 dwg, 1 tbl

Description

The invention relates to the field of chemical current sources, and in particular to the technology for the production of lead-acid batteries (Lead Acid Batteries), designed for small engines and medium starter conditions, but with increased reliability in cycles for moderate operating conditions in 30-50 % DOD (DOD - charge and discharge in% of the declared capacity for a 20-hour discharge mode) is at least two times higher than that of batteries (Flooded Lead Acid - FLA, purely starter), for batteries made by GEL (Gelled Electrolite ), as well as FLA dual-use batteries (One Hundred Terno / Traction batteries with liquid electrolyte), and a class of EFB (Enhanced Flooded Battery - enhanced flooded batteries), capable of operating in vehicles equipped with the system "start-stop". In this case, lead-acid batteries can be performed both in a sealed version and with an additionally thickened electrolyte.

The European car fleet is changing at an unprecedented rate. Legislators have established stringent requirements requiring automakers to reduce CO ₂ emissions to 130 g / km by 2015 and to 95 g / km by 2021, i.e. reduce CO ₂ emissions by 40% compared to 2007. Such tasks force car manufacturers to develop much more fuel-efficient cars with modern batteries and advanced electric drive capabilities (Start-Stop system, battery management system and smart generators), due to which charging is no longer performed continuously. These new technologies are based on the advanced AGM (Absorbent Glass Mat) batteries. The AGM separator is a combination of an AGM fiberglass with an acid resistant binder. This lead acid battery manufacturing technology was created in the early 1970s. EFB technology is also used for the initial assembly of auto assembly lines.

The idea of producing micro hybrid cars dominates Europe. Despite the fact that cars equipped with conventional powertrains still make up the majority of the fleet, the percentage of Start-Stop cars is growing rapidly from year to year.

Since the requirements for reducing fuel consumption and minimizing emissions of harmful exhaust gases by cars have substantially increased, the operating conditions of a lead car battery have also changed significantly.

One example of such operating conditions is charge control. Typically, a rechargeable automotive lead battery is charged when the generator is driven by an engine, as is the case with power being supplied to other electrical equipment. Therefore, the lead battery is always in a recharge state, which, of course, leads to increased fuel consumption. In this regard, car manufacturers are currently proposing to control the charge of the lead battery, respectively reducing fuel consumption and minimizing emissions of harmful exhaust gases.

There are known the so-called charge control systems, intelligent charging systems, the algorithm of which allows you to diagnose the condition of the battery by its internal resistance and voltage at the terminals, which requires recharging of the lead battery. The lead battery is only recharged when this condition is detected, thereby overcharging the battery and eliminating fuel consumption.

However, if the lead battery is recharged only when it is found that recharging is necessary based on the results of detecting the aforementioned partial charge state (SEC), then the ability to recharge the lead battery will be limited, so that the lead battery will always be in the SEC . However, if a lead storage battery is used in this partial charge state and at the same time has a low or standard recharging efficiency, it will be very quickly brought into a state of chronic undercharging.

For new generation batteries, it remains relevant to increase resistance to deep discharges and increase service life at higher operating temperatures due to a denser layout of the engine compartment of modern cars and reduced access to a cooling air battery. Therefore, one of the main requirements for starter batteries was the provision of their corrosion resistance at high operating temperatures.

Thus, there are contradictions in the instantaneous requirements for modern starter batteries, which have to be overcome. On the one hand, the battery should have the maximum starting power: it is a thin electrode, a separator of minimum thickness with a minimum body and rib size, a developed contact surface of the grating with the active mass and its high porosity, and on the other hand, high corrosion resistance of the gratings, and paste resistance to floating in deep charge-discharge cycles. This requires a heavy electrode grid with a rigid frame, a thick electrode, a puncture-resistant separator, and, in general, a low level of operating costs (maintenance-free) is necessarily required due to low self-discharge, reduced gas emission and water consumption.

Known sealed lead-acid battery containing an electrode block consisting of negative and positive electrodes separated by separators and a sulfate electrolyte, characterized in that only the positive electrodes contain a gel-like sulfate electrolyte in the pores, and the remaining volume of the battery contains a sulfate electrolyte in a liquid state (RF patent No. 2285983, IPC H01M 10/10).

According to the patent, in order to increase the service life of the lead battery, it is proposed to strengthen the active mass of the positive electrode and thereby increase the efficiency of its use while maintaining a low internal resistance of the battery due to the fact that a gel-like sulfate electrolyte is formed in the pores of the positive electrodes, and the remaining volume of the battery contains sulfate electrolyte in a liquid state. The consequence is an increase in capacitive characteristics, and therefore, an increase in battery life by 1.4 ÷ 1.6 times. It is proposed to use a silicate solution with a low content of sodium ions as a thickener for a lead-acid battery.

The specified technical solution can be applied only to a limited type of battery structures, which narrows the range of its use.

Known lead battery containing a block of negative electrodes and a block of positive electrodes separated by separators, on which the sides facing the positive electrodes are made of vertical ribs, and placed in a vessel (monoblock) filled with electrolyte, characterized in that the lattice of positive electrodes made with horizontal cores, and on the sides of the separators facing the positive electrodes, horizontal ribs of which is equal to or less than the number of horizontal cores in the grid of the current collector of the positive electrode, and the number of horizontal ribs in the lower part of the separator is greater than in its upper part, and their location on the surface of the separator coincides with the location of the horizontal cores in the grid of the collector of the positive electrode (RF patent No. 2362240 dated 12/04/2006).

The technical result of the invention according to the patent is the prevention of creeping and creeping of the active mass of positive electrodes, ensuring the operability and predetermined technical characteristics of the batteries during operation, increasing their service life. In this case, the main reason for the floating and creeping of the active mass of positive electrodes is the pressure force that has reacted in the chemical reaction of the active mass of the upper parts of the surface of the positive electrode to the lower ones during operation of batteries discharged by more than 25% of the nominal capacity. The magnitude of this pressure increases as the battery discharges.

In the description of the invention, it is noted that the aging and ablation processes of the active mass usually occur uniformly over the entire surface of the electrode. Other processes, however, are unevenly distributed along the surface of the positive electrode. An example is the gradual creep of the active mass from the upper zones of the electrode and its accumulation in the lower ones. Creeping is sometimes observed in high batteries and is not the result of a simple swelling of the active mass. It can be caused by concentration changes in the electrolyte: a more concentrated and heavier solution formed during charging or discharging accumulates in the lower part of the battery monoblock, pushing the lighter layers upward, as a result of which the liquid seems to separate. As a result of this condition, the course of the electrode processes in the lower and upper parts of the electrodes changes: in the upper conditions, favorable for the dissolution of the active substance, in the lower - its deposition.

Creeping or moving of the active mass causes accumulation of excess mass in some areas, which is not always associated with an increase in the thickness of the electrode and can lead to a decrease in porosity. In this case, the contact surface with the electrolyte decreases, diffusion difficulties and effective conductivity in the pores increase, i.e. the general working conditions of the active mass and its utilization rate are deteriorating. As a result, in some places a complete cessation of the active mass, i.e. her passivation.

The disadvantage of this technical solution is the binding design of the separator to the structural design of the electrode array. The presence of transverse ribs on the separator will delay large bubbles of the resulting gases from floating, which will block part of the useful area of the electrodes, increasing the internal resistance of the battery.

Known lead-acid battery containing a housing closed in the upper part by a lid and divided into compartments in which the batteries are located, connected in series using interconnects, each battery consists of a block of bipolar electrodes separated by separators and electrolyte, the electrodes consist of down conductors and active mass, the leads of the positive electrodes are made of lead-tin-calcium alloy with silver additives, characterized in that the alloy is positive contains down conductors, wt. %: 0.7 ÷ 1.5 Sn; 0.04 ÷ 0.06 Ca; 0.001 ÷ 0.015 Ag; 0.015 ÷ 0.05 Al, lead - the rest, the active mass of positive and negative electrodes is covered with fixing layers of a porous acid-resistant material (RF patent No. 2233510 of 08.08.2002).

The technical result of the invention according to the patent is reliable adhesion of the active mass of the electrodes to the down conductors, protecting the active mass from cracking and shedding, which leads to an increase in the service life of the lead-acid battery. The battery down conductors are made of perforated lead alloy tape. The presence of positive tin down conductors in the alloy of 0.5-1.5% prevents the formation of a passivating layer between the down conductors and the active mass, which ensures high resistance of the electrodes to deep discharges and the possibility of their subsequent charge. With a smaller amount of tin in the alloy (less than 0.5%), a passivating layer is formed between the down conductors and the active mass. With a larger amount of tin in the alloy (more than 1.5%), the time of natural “aging” and hardening of the tape from such an alloy increases, which leads to an increase in the duration of the technological process of manufacturing the electrodes. The presence in the alloy of positive calcium down conductors in an amount of 0.04-0.06% provides good mechanical strength of the down conductors, their sufficient corrosion resistance at high operating temperatures, as well as reliable adhesion to the active mass. A decrease in the amount of calcium in the alloy (less than 0.04%), increasing the corrosion resistance, leads to a deterioration in the mechanical properties of down conductors and a deterioration in adhesion to the active mass, which leads to a reduction in the battery life. An increase in the amount of calcium in the alloy (more than 0.06%) reduces the corrosion resistance of positive down conductors. Silver in an amount of 0.001-0.05% increases the corrosion resistance, hardness and strength of down conductors. With less silver in the alloy (less than 0.001%), the effect of its addition disappears. An increase in the amount of silver in the alloy (more than 0.05%) does not lead to a noticeable improvement in the quality of down conductors and is not economically feasible. Aluminum in an amount of 0.01-0.05% can reduce the loss (burnout) of calcium during melting of the alloy, forming a protective surface layer in the melt. The presence of aluminum makes it possible to reliably control the specified amount of calcium in the alloy, thereby providing properties determined by calcium.

The fixing layers of a porous acid-resistant material covering the active mass increase its resistance to cracking and shedding both during the manufacture of the battery and during its operation. Moreover, the material of the fixing layers is characterized by high porosity and air permeability, it is well wetted by an electrolyte - an aqueous solution of sulfuric acid, without interfering with the latter's access to the active mass of the electrodes. The high porosity and air permeability of the material of the fixing layers creates the conditions for free exit from the pores of the active mass of gas bubbles, which are formed in small quantities during the recharging process.

The lead-acid storage battery according to the patent of the Russian Federation No. 2233510 is the closest solution in technical essence and the achieved result and is taken as a prototype.

The prototype is based on a comparable task - the improvement of a lead-acid battery, in which, due to a change in the chemical composition of the alloy of positive current leads and the introduction of additional elements, reliable adhesion of the active mass to the current leads is ensured. This problem is solved by the fact that the collectors of the positive electrodes are made of lead-tin-calcium alloy with silver additives. The down conductors of the claimed battery are made of perforated tape (ExMet technology) of the lead alloy specified in the composition formula.

In the prototype, in general terms, without disclosing the type of materials used, an embodiment of the protective coating of the active masses and the method of its application are given, which makes it impossible to repeat the design according to the descriptive part of the claims, which should guarantee a technical result. To achieve the claimed effect - to ensure an increase in the life cycle of the battery and reduce its internal resistance due to changes in the chemical composition of the alloy of positive collectors, the prototype does not consider the tin content in the alloy of the lattice above 1.5% under the unjustified pretext of increasing the time of natural "aging" and hardening of the tape from such an alloy, which leads to an increase in the duration of the technological process for the manufacture of electrodes. In fact, this is not so, because an increase in the concentration of tin in the alloy in itself reduces the percentage of elongation of the alloy and increases the tensile strength. “It was found that the addition of tin only accelerates the aging process, as a result, alloys acquire a hardness already a day after casting, sufficient for their practical application. Tin also increases the strength and fluidity of the alloy ”(Rusin A., Khegai L., Tokarchuk S. Lead alloys for modern batteries. Theory and practice. Vladivostok: Dalnauka, 2008, 221 pp. ISBN 978-5-8044-0892-4) . The harmful effect of silver in the alloy on the decrease in the adhesion of the paste to the positive lattice electrode is also not indicated, namely, that silver significantly increases the corrosion resistance of the alloy, which prevents a good corrosion surface adhesion of the paste and lattice at the stage of steam maturation of the plates in the curing chambers.

The role of the structural design of the separation separator to achieve the goals, as well as the option to achieve improved adhesion of the active mass to the down conductors due to the composition or method of manufacturing the active mass itself, is not reflected and was not considered in the prototype, this possible part of the technical solution is absent in the prototype, and its mechanism not considered. The present invention provides an answer to this question.

The technical result of the present invention is to eliminate the disadvantages of the prototype and improve such consumer properties of the battery as the service life during constant operation under conditions of partial charge SCH, reliability with increased starting load on vehicles equipped with Start-Stop systems, achieved by better active clutch the mass of electrodes with down conductors, protecting the active mass from cracking and shedding during the life cycle, reducing the boundary irreversibly calcination of the electrode array, an increase in the efficiency of the active masses, a decrease in the stratification of the electrolyte in the cells, and a deep irreversible sulfation of the active masses of the electrodes.

The technical result is achieved by solving the technical problem, which consists in creating a lead-acid rechargeable battery containing a housing closed in the upper part by a lid and divided into compartments in which the batteries are located, connected in series using inter-cell connections (MES), each battery consists of a unit of different polarities electrodes separated by separators and electrolyte, the electrodes consist of down conductors and active mass, the leads of the positive electrodes are made of lead-tin o-calcium alloy with additives of aluminum and silver, the active mass of positive and negative electrodes is covered with fixing layers of a porous acid-resistant material, characterized in that the alloy of positive current collectors additionally contains bismuth Bi 150 ÷ 500 ppm, other components are contained in wt. %: Sn 2.0 ± 0.1%; Ca 0.04 ± 0.005%; Al 0.005 ± 0.01%; Ag 0.007 ÷ 0.04%, lead - the rest, and the alloy of bridges (MES), contains the main components: Sn 3 ± 0.1%; Sb 1.0 ± 0.1%; As 0.055 ± 0.015%; Se 0.008 ± 0.001%; Cu 0.013 ± 0.002%; lead - the rest, the additional active mass of positive and negative electrodes completely covers the lattice nodes on both sides, the fixing layers of a porous acid-resistant material are indestructible during the formation and during the life cycle of a pasting sheet made of a mixture of glass microfibers and synthetic fibers, with specific surface of at least 1.5-2.0 m ² / g, separation separators are envelopes of high molecular weight polyethylene with double-sided vertical ribs or laminated with fiberglass on the inside of the envelope facing the positive electrode.

The practice of designing and testing mixed-cycle batteries and batteries operating with Start-Stop systems shows that the main reasons for their failure are: critical loss of water by electrolyte, growth of the positive electrode frame and corrosion of its veins, loss of conductivity of electrodes at the boundary the lattice / active mass due to calcination (formation of an indestructible film of calcium sulfate at the interface), which is typical only for lead-calcium maintenance-free batteries.

Currently, for lead-acid batteries having a prismatic design of electrode blocks, there is virtually no alternative to lead-calcium alloys, because only they can provide low and ultra-low water consumption. It is possible to successfully deal with the harmful phenomenon of borderline calcium sulfation by introducing tin positive electrode gratings into the alloy, while the calcium content must be kept at the minimum limit at which the electrode is still aged, i.e. there is a set of strength and a decrease in the relative elongation of the alloy during storage. As one example of such an alloy, an alloy of the prototype was presented (RF patent No. 2233510).

However, the present invention proposes to use for these purposes an improved alloy composition, significantly different from the prototype both in the list and in the content of the main components. Indeed, the maximum corrosion properties of the lead-tin-calcium alloy are achieved even when the tin content in the alloy is within 1.5%, but the best properties of the alloy for resistance to deep discharges lie in the range of higher concentrations, 2.0-3.0% . At such tin concentrations in the alloy, a dense layer of calcium sulfate is not formed at the grate / paste interface, an oxidation product of the grating material, which, due to its low electrical conductivity, reliably blocks active masses, causing the phenomenon of deep sulfation even in batteries with a short service life. However, above 2%, increasing the tin in the grates also does not make sense, since a slight further improvement in the properties of the alloy is not compensated by the added cost of tin, and under normal conditions, the solubility limit of tin in lead also lies in the range below 3%, which imposes its own additional limitation. There is no difficulty at this concentration (2%) and an increase in the ripening time of the alloy, since with increasing tin concentration, the tensile strength of the alloy automatically increases, the percentage of elongation decreases, and the technological process does not lengthen.

The upper threshold of calcium in the prototype is indicated as 0.06%, it is necessary for alloys with a tin concentration below 1.5%, but completely redundant for alloys with 2.0% tin. An increase in tin content to 2.0% made it possible to reduce calcium to 0.04%, which significantly improved the battery's ability to withstand deep discharges, even with thin gratings of the positive electrode.

According to the prototype, the aluminum in the strip alloy is maintained within the range of 0.01-0.05%, which reduces the loss (burnout) of calcium during melting of the alloy, forming a protective surface layer in the melt. The presence of aluminum makes it possible to reliably control the specified amount of calcium in the alloy, thereby providing properties determined by calcium.

Currently, the optimal range of aluminum content in the alloy lattice has changed. Modern methods for producing a lead-calcium strip are associated with a very insignificant yield of recyclable waste and, consequently, calcium burnout, while the high aluminum content in the alloy of the gratings is not harmless in the production process for the battery itself, since leads to a large percentage of losses of the molten alloy in the formed oxidized crosses (slag that floats to the surface of lead and which is the oxidized form of lead and metals that are part of alloys with inclusions of the metal fraction of the alloy) due to the very limited solubility of aluminum in lead when the alloy temperature decreases below 400 ° C.

It is also known that the formation of aluminum sulfate upon dissolution of aluminum from the surface layer of the gratings also reduces their corrosion resistance. Some manufacturers of modern equipment for manufacturing lattices of perforated tape (strip) of lead-calcium alloy (ExMet technology), for example, a rotary expander (BTS Cominco expander), generally do not provide for the use of aluminum in the working alloy of the strip in the basic version. For these reasons, the working range of the aluminum content in the alloy of the present invention has been significantly changed and lies outside the range specified in the prototype.

In the prototype, the question of the possible content of lattices of a component such as bismuth in the calcium alloy remained completely unlit. Bismuth is an indispensable lead metal satellite. It is known that the battery industry imposes stringent requirements on the content of foreign impurities in lead and lead alloys, including bismuth, whose content under these requirements should not exceed thousandths of a percent. The process of purification of lead from bismuth is extremely time-consuming, associated with a large consumption of reagents, an increase in lead refining time and the release of additional recycled waste (sludge). The resulting removal is difficult and costly to process, significantly reduce the yield of lead from the refining operation. All this prompted many researchers to carefully study the effect of bismuth in gratings and its salts in lead oxides, which are used for the production of active masses, on the characteristics of a lead battery (A. Rusin, L. Khegay, and S. Tokarchuk. Lead alloys for modern batteries. Theory and practice. Vladivostok: Dalnauka, 2008, 221 pp. ISBN 978-5-8044-0892-4. Chapter 5). In connection with the practicable expansion of the bismuth content in the alloys of positive current leads of lead-acid batteries, it was found that the potential of the positive electrode with the addition of bismuth decreases during the discharge much more slowly. In lead batteries, especially with an adjustable valve, 0.05% of bismuth introduced into lead oxide increases the initial capacity and increases the service life in cycles. Bismuth in lead oxide does not affect the loss of water in conventional batteries. Considering that bismuth, which is a part of the alloy of positive current leads, can be ionically transferred to the active mass of negative electrodes, the charging characteristics of negative electrodes were studied depending on the content of bismuth oxide in them. It was found that the decrease in the electrode potential during discharge occurs at a lower rate when the bismuth content in the paste is 0.01%. All this, including economic feasibility, allows us to consider the natural (background) bismuth content in battery alloys in the range 150–500 ppm as a useful component of these alloys.

As a rule, little attention is paid to the chemical composition of the alloy, from which jumpers and all other conductive elements of the battery are cast, although the role of this alloy in the total water consumption and battery maintenance is very significant. In the process of working on the present invention to achieve the claimed technical results, a new formulation of such an alloy was worked out - solder, which allows to solder and shape the ears of gratings (from low-melting lead-calcium alloy containing up to 2% tin) into the bridges of the blocks of electrode plates on existing assembly line equipment without finalizing it or installing a new one.

The tin in this alloy, first of all, increases its tensile strength, eliminates the tendency to crack formation, which characterizes almost all alloys with a low antimony content, improves casting properties and, most importantly, reduces the melting and solidification temperatures of the alloy, which allows the use of high-performance low-temperature alloys Pb-Sn-Ca alloys with a high tin content, without the risk of burning out the ears of the plates when they are soldered into a common block bridge with an inter-element connection (MES).

The optimal set of properties for soldering the ears of plates of high tin alloy will be the alloy corresponding to the following composition: Sn 3 ± 0.1%; Sb 1.0 ± 0.1%; As 0.055 ± 0.015%; Se 0.008 ± 0.001%; Cu 0.013 ± 0.002%; lead is the rest.

The lead-acid storage battery according to the present invention is also characterized in that the paste sheet is glued to all opposite surfaces of the electrode plates of both signs, the coating being applied during the application of the active mass to the plate grid until it rolls into the paste, with a residual moisture content of W = 10- fourteen%.

The web material is selected according to several criteria:

- the fabric should have maximum porosity and strength of the structure of the micelles themselves, forming a non-woven carpet;

- the specific surface of the web is selected in the range of 1.5-2.0 m ² / g, and the web itself should not change its transverse geometry during the spreading process.

The lead-acid storage battery according to the present invention is also characterized in that it is assembled using expanded expanded gratings from lead-tin alloys with calcium, the gratings are made according to the technology of rotary cutting and subsequent expansion, which eliminates the formation of microcracks in the nodes of the gratings, additionally the gratings have reinforced lower frame, and the weight of the positive grating alloy is selected so that it is not less than 4.7 g / per 1 Ah of electrode capacity, calculated according to a 20-hour r Bench Press discharge - (C _20).

Under other different conditions, the most important factor affecting the corrosion resistance of the plates, water consumption with constant recharging, the growth of the electrode frame due to oxidation of the alloy, is the massiveness of the electrode array.

To identify the degree of significance of this factor, experiments were carried out using the following procedure.

Charge method

A fully charged battery (battery) is prepared as follows. After the holding period, a break at 25 ° C ± 2 ° C, the battery is charged 25 ° C ± 2 ° C, 24 hours at 16.00 V ± 0.10 V with current limitation Imax = 5I20 (five current values of the 20-hour discharge mode).

Basic water consumption test

After charging the battery in accordance with paragraph "Charge method" the batteries must be washed, dried and weighed with an accuracy of ± 5 g, the weight is recorded.

The batteries are maintained at a temperature of 40 ± 2 ° C for 8 hours, after which they are charged at a constant voltage of 14.40 V ± 0.05 V (measured opposite the battery terminals) for 28 days without adding water.

Immediately after a recharge period, the batteries are washed, dried and weighed with an accuracy of ± 5 g. The weight is recorded.

Immediately after weighing, the recharge sequence is repeated at a temperature already of 70 ± 2 ° C.

Requirements

For T ° C = 40 ° C, the maximum water loss should be less than 1.0 g / Ah C20, e ± 0.1 g / Ah C20, e.

For T ° C = 70 ° C, the maximum water loss should be less than 6.0 g / Ah C20, e ± 0.6 g / Ah C20, e.

For the experiment, control batteries made of positive calcium alloy gratings having a thickness of 0.89 mm and a weight of 41.2 g per electrode were taken. 82 g of paste were dry-weighted into such a grate. The calculated capacity of one electrode plate was 9.723 Ah for a 20-hour discharge mode C20, e. The weight of the positive grating alloy per 1 Ah of the calculated capacity was 41.2 / 9.723 = 4.237 g / per 1 Ah. In the second group, the batteries were assembled from gratings that had an initial strip thickness of 1.0 mm and a weight of 45.7 g. The weight of the paste and the spreading area completely corresponded to the batteries of the control group. The weight of the positive grating alloy per 1 Ah of the calculated capacity was 45.7 / 9.723 = 4.7 g / 1 Ah. The thickness of the grating in the experimental group differed from the control only by two technological tolerances. This is the smallest difference that can be tracked during production with a high degree of certainty.

The results are shown in the Table.

It is clear that the established criterion is technologically achievable in production, does not require new equipment and allows you to achieve your goal.

The lead-acid storage battery according to the present invention is also characterized in that the ratio of the total weight of the unformed dry active mass of the positive half block of plates to the total dry weight of the unformed active mass of the negative half block of plates should be within the specified limits when calculated according to the following empirical formula:

where n is the number (+) of electrodes in the semiblock; m is the number of (-) electrodes in the semi-block; Qn is the weight of the dry active mass of the unformed positive electrode; Qm is the weight of the dry active mass of the unformed negative electrode; η (+) - efficiency of the active mass of the positive electrode (0.5255 - recommended value); η (-) is the efficiency of the active mass of the negative electrode (0.5800 is the recommended value).

To achieve the claimed technical result of the present invention and in order to ensure a minimum water consumption, the indicated scheme for calculating the necessary ratio of positive active to negative mass is proposed, taking into account the assembly of the semiblock plates. The novelty lies in the fact that it is proposed to calculate the overlapping area of the plates of both signs, which is very important due to the low scattering ability of the sulfuric acid electrolyte, and taking into account the small incorporated excess of negative mass necessary for the binding of oxygen formed in the final stage of the charge of the anode semiblocks, on the undeformed active mass of negative plates. Both the formula itself and the established, put into practice criterion for the formation of PAM / NAM (the ratio of the weight of the positive active mass to the negative, plates of one electrode block) have novelty at the design stage of the battery design.

The lead-acid storage battery according to the present invention is also characterized in that the material of the separation separator is laminated from the side facing the surface of the electrodes of the positive half block of the plates with a layer of glass fiber with a thickness of 0.2 ÷ 0.4 mm, and a free gap along the working width of the battery cell between the electrodes is selected selection of the height of the longitudinal ribs of the separator so that the designed free gap on one side of the unformed electrode of any sign would be within 0, 1 ± 0.015 mm.

In the process of manufacturing the battery and its life cycle, processes are continuously ongoing associated with a natural change in the thickness of the active mass layer. So, during the initial filling of the battery with an electrolyte of sulfuric acid, the main reaction of sulfation of free lead oxide proceeds:

PbO + H ₂ SO ₄ = PbSO ₄ + H ₂ O.

If initially a lead atom was bound to only one oxygen atom, then after sulfation, one oxygen atom and one sulfur atom fall on one lead atom. Naturally, the density of such a compound will be less, and the volume occupied by the new substance will be much larger, because the number of lead atoms does not change. And further, in the process of charging, the volume occupied by the active mass of the electrodes decreases again, and this difference is much larger for the negative electrode.

PbSO ₄ + PbSO ₄ + 2H ₂ O = Pb + PbO ₂ + 2H ₂ SO ₄ .

To ensure the necessary freedom when changing the volume occupied by the active mass of the electrodes, they conduct the design, immediately laying the necessary gaps.

The lead-acid battery according to the present invention is also characterized in that its housing is closed on top with a sealed cover equipped with a float indicator of electrolyte density, in the case of a battery in the versions FloodedLeadAcid (FLA) or EnhancedFloodedBattery (EFB) or a common battery cell cover having a single gas outlet with plug, with threaded holes for non-loosening plugs or with plug block or in VRLA version (ValveRegulatedLeadAcidbatteries - valve-regulated lead-in slotnyh batteries) and Labyrinth bar or duplex cover. The choice of body parts is determined primarily by the requirements to achieve maximum eradicability of the electrolyte and the difficulty of access to the battery cells.

All of these structures have high protection against electrolyte flow when the battery is turned over or when installed on an edge, and an EFB (Enhanced Flooded Battery - an advanced liquid electrolyte battery) battery does not require replenishment of the electrolyte over the entire life cycle, therefore, plugs can be designed , making it most difficult to turn them off in order to avoid unauthorized topping up or getting a chemical burn.

The method for preparing lead active masses for a lead-acid storage battery according to the present invention is characterized in that instead of water and a sulfuric acid electrolyte with a density of 1.4 g / cm ³ , initially prepared sulfuric acid electrolytes are used for the manufacture of pastes of both signs for positive and negative active masses :

- electrolyte of positive active mass, the density of the solution 1,115 g / cm ³ ; the acid concentration in the solution reduced to 20 ° C is 186.8 g / l, or 16.76%; the flow rate of the solution is 0.193 liters per 1 kg of lead oxide;

- electrolyte of negative active mass, the density of the solution is 1.105 g / cm ³ ; the acid concentration in the solution reduced to 20 ° C is 170.2 g / l, or 15.41%; the flow rate of the solution is 0.1608 liters per 1 kg of lead oxide,

moreover, the speed of loading lead oxide into the mixer for mixing with the electrolyte is selected as high as possible, and the temperature of the beginning of the forced cooling of the mixture is set not lower than 65 ° C.

In the prototype, there are completely no restrictions regarding the method and type of active masses used for the battery, which allows to achieve increased resistance to deep discharges and increased service life. So, it is known that in almost any lead pastes to the touch and rubbing with fingers, micro-lumps, the so-called groats, are found. A study of the microstructure of grains by sections in paraffin showed that they are of two types in structure: spherical formations uniformly penetrated by lead sulfate, or such formations in the middle of which there is lead powder. In some cases, the grains are loose with shells inside, in others, dense. Those. one type of cereal is formed from an oxide that is not in contact with sulfuric acid electrolyte, but coated with “glaze” from a layer having an excess of lead sulfate, and another type of cereal consists of aggregates with a very high content of lead sulfates, formed due to local excess of acid due to its imperfection introduction and ineffective distribution comb. In any case, the grits significantly worsen the operational properties of the active masses, both in terms of capacity return per unit weight and in terms of its service life.

Significantly reduce the formation of cereals in the active mass became possible by changing the method of introducing lead oxide into a dilute solution of sulfuric acid electrolyte, switching to the following sequence when preparing active masses: water - special additives - sulfuric acid electrolyte - lead oxide. The traditional scheme provides a different loading order: water - lead oxide - special additives - sulfuric acid electrolyte.

The design of the lead acid battery of the present invention is shown in the drawing.

A lead-acid battery contains the following components and parts: battery case 1, cover 2, plug 3, terminal plate 4, electrode eye (plates) 5, interconnect (MES) 6, block bridge 7, envelope separator 8, electrode ( plate; electrode plate) 9, grating (down conductor) 10; a semiblock of electrodes 11 (contains plates of only one polarity), a float indicator 12 of the electrolyte density, and a plug for a single gas duct 13.

The technological assembly route of the unformed battery of the present invention schematically includes the following sections:

1. The manufacture of lead-calcium strips of the desired chemical composition for the positive and negative lattice;

2. Perforation of strips and their stretching into a continuous tape of future gratings;

3. Preparation of active masses based on lead oxide according to the specified special technology and their smearing into grids with simultaneous surface protection with a special indestructible fabric;

4. Separation of the pasted tape into separate electrodes and their drying in a steaming chamber;

5. Assembly of the plates into blocks and their desoldering with a special alloy on the automatic machine for the formation of jumpers of the ears of the plates;

6. Punching interblock holes in the battery housing and laying in the cells of the assembled blocks of electrodes;

7. Welding MES blocks between each other through perforated holes. Six batteries are connected in series, forming a 12-volt battery;

8. Weld cap;

9. Welding of bushings with extreme battery terminals (born);

10. Filling the battery with an electrolyte containing all the necessary additives;

11. The formation of the battery according to a special algorithm;

12. Topping up with electrolyte, washing, drying, installation for sedimentation (quarantine);

13. Testing, labeling, packaging, shipping to the consumer.

The technical solutions indicated in the present invention should be used together to guarantee achievement of the set goal. Separate mutual restrictions in the design of the battery, even theoretically, cannot be applied separately. So, for example, a high-tin alloy of gratings can be used only with a high-tin alloy of bridges and MES, otherwise the difference in the melting points of the alloys will make it practically impossible to achieve high-quality soldering.

Technical appraisal and economic benefits achieved by using the batteries of the present invention are to increase the service life by more than two times as compared to a conventional unattended battery, ensure high starting currents throughout the battery life cycle, on vehicles equipped with systems Start-Stop, improved by 20-30% speed of charge reception at low temperatures, fuel economy and, as a result, reduction of CO ₂ emissions. The battery is an excellent compromise for cars manufactured using technologies aimed at saving the environment (Start-Stop, hybrid, controlled charge), as these cars have great demands on battery reliability.

Claims (7)

1. A lead-acid rechargeable battery containing a housing closed in the upper part by a lid and divided into compartments in which the batteries are located, connected in series using interconnects, each battery consists of a block of bipolar electrodes separated by separators and electrolyte, the electrodes consist of down conductors and active mass, the collectors of positive electrodes are made of lead-tin-calcium alloy with the addition of aluminum and silver, the active mass of positive and negative nyh locking electrodes covered with layers of a porous acid resistant material, characterized in that the positive electrodes of the alloy additionally contains bismuth Bi 150 ÷ 500 ppm, other components contained in an amount, by weight. %: Sn 2.0 ± 0.1%; Ca 0.04 ± 0.005%; Al 0.005 ± 0.001%; Ag 0.007 ÷ 0.04%, lead - the rest, and the alloy of bridges of interelement compounds (MES) contains the main components: Sn 3 ± 0.1%; Sb 1.0 ± 0.1%; As 0.055 ± 0.015%; Se 0.008 ± 0.001%; Cu 0.013 ± 0.002%; lead - the rest, the additional active mass of positive and negative electrodes completely covers the lattice nodes on both sides, the fixing layers of a porous acid-resistant material are indestructible during the formation and during the life cycle of a pasting sheet made of a mixture of glass microfibers and synthetic fibers, with specific surface area of at least 1.5 ÷ 2.0 m ² / g, dividing separators are envelopes of high molecular polyethylene having located thereon bilateral vertical ribs or fiberglass laminated with the inner side of the envelope facing the positive electrode. 2. The lead-acid storage battery according to claim 1, characterized in that the pasting sheet is glued to all opposite surfaces of the electrode plates of both signs, the coating being applied in the process of applying the active mass to the plate grid until it rolls into the paste, with residual moisture W = 10-14%. 3. The lead-acid storage battery according to claim 2, characterized in that it is assembled using expanded expanded gratings from lead-tin alloys with calcium, the gratings are made according to the technology of rotary cutting and subsequent expansion, which eliminates the formation of microcracks in the nodes of the gratings, additionally, the gratings have a reinforced lower frame, and the weight of the positive gratings alloy is selected so that it is not less than 4.7 g / 1 Ah of the electrode capacity calculated according to the 20-hour discharge mode - (C ₂₀ ). 4. A lead-acid storage battery according to claim 3, characterized in that the ratio of the total weight of the unformed dry active mass of the positive half block of plates to the total dry weight of the unformed active mass of the negative half block of plates should be within the specified limits when calculated according to the following empirical formula:

where n is the number (+) of electrodes in the semiblock; m is the number of (-) electrodes in the semiblock; Qn is the weight of the dry active mass of the unformed positive electrode; Qm is the weight of the dry active mass of the unformed negative electrode; η (+) - efficiency of the active mass of the positive electrode (0.5255 - recommended value); η (-) is the efficiency of the active mass of the negative electrode (0.5800 is the recommended value). 5. The lead-acid storage battery according to claim 1, characterized in that the material of the separation separator is laminated from the side facing the surface of the electrodes of the positive half block of plates with a layer of glass fiber with a thickness of 0.2 ÷ 0.4 mm, with a free gap along the working width of the cell the battery between the electrodes is selected by selecting the height of the longitudinal ribs of the separator so that the designed free gap on one side of the unformed electrode of any sign is within 0.0 ± 0.15 mm. 6. Lead-acid battery according to any one of paragraphs. 1-5, characterized in that its case is closed on top with a sealed cover equipped with a float indicator of the density of the electrolyte, in the case of the battery in the options FloodedLeadAcid (FLA) or EnhancedFloodedBattery (EFB) or a common battery cover of the battery having a single gas outlet with threaded openings for non-loosening plugs or with a plug block or in the VRLA version (Valve Regulated Lead Acidbatteries - valve-regulated lead-acid batteries) and with a labyrinth strip or duplex cover. 7. A method of preparing lead active masses for a lead-acid storage battery, characterized in that instead of water and a sulfuric acid electrolyte with a density of 1.4 g / cm ³ , originally prepared sulfuric acid electrolytes are used for the manufacture of pastes of both signs for positive and negative active masses :
- electrolyte of positive active mass, the density of the solution 1,115 g / cm ³ ; the acid concentration in the solution reduced to 20 ° C is 186.8 g / l, or 16.76%; the flow rate of the solution is 0.193 liters per 1 kg of lead oxide;
- electrolyte of negative active mass, the density of the solution is 1.105 g / cm ³ ; the acid concentration in the solution reduced to 20 ° C is 170.2 g / l, or 15.41%; the flow rate of the solution is 0.1608 liters per 1 kg of lead oxide,
moreover, the speed of loading lead oxide into the mixer for mixing with the electrolyte is selected as high as possible, and the temperature of the onset of forced cooling of the mixture is set not lower than 65 ° C.

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