Patent Publication Number: US-2007111043-A1

Title: Method of forming lead-acid batteries and plant for implementing said method

Description:
This invention concerns a rapid method for forming lead-acid batteries, of the type used mainly, but not only, to start thermal engines.  
      An important stage in the process for manufacturing lead-acid batteries is the so-called “forming” of the plates, where the battery&#39;s discharging and recharging reactions take place due to the electrochemical conversion of the active matter they contain, which transforms the chemical energy into electrical energy and vice versa.  
      When they are manufactured, the plates are inert, or inactive; to make them active, the plates are submitted to a forming procedure that transforms the inactive lead oxide and lead sulfate into metallic lead and lead dioxide, which are the active constituents of the negative and positive polarity plates, respectively.  
      Forming consists essentially in submitting plates of opposite polarity to a charging procedure with a direct electric current in a solution of sulfuric acid diluted with water (the electrolyte) and this can be done before or after assembling the plates in the battery.  
      In the former case, we speak of forming in the tank, in the latter of forming in the case.  
      In practice, forming in the case is used to form the engine starter batteries—and generally for all small batteries, regardless of their application—mainly to contain costs.  
      A preferred method involves filling the batteries with a diluted electrolyte, completing the forming process, then removing and replacing the forming electrolyte, which will have become more concentrated, filling the battery once again with an electrolyte at a concentration very similar to the one used in the battery&#39;s operation.  
      This method is also called “forming in the case with two acids” to distinguish it from the method using one acid, where the forming electrolyte used is more concentrated so that, by the end of the forming process, it reaches the right concentration for the battery&#39;s operation, thereby simplifying the process.  
      Technology has always made efforts to accelerate the forming process and the only effective way to do so is to increase the charging current in order to reduce the forming time for the same amount of electric energy delivered to transform the inactive into active masses.  
      There is a limit, however, to how much the current can be increased, imposed by the ability of the plates (especially the positive plate) to withstand the forming charge, and particularly the increase in temperature induced by the heat generated by the exothermal reactions in the forming process and the Joule effect caused by the flow of current  
      A particularly large amount of heat is generated during the forming of starter batteries “in the case” because of the high ratio of the mass of lead oxides that have to be transformed from inactive into active with respect to the amount of forming electrolyte in the battery.  
      The state of the art has attempted to overcome the problem by using special oxide formulations for the positive plate and using very diluted forming acids, opting for forming with two acids to improve plate formability and resorting to even sophisticated cooling systems to control the increase in temperature during the forming process.  
      Even so, forming times have been unable to drop below 12-15 hours.  
      Another problem relating to battery forming concerns the hydrogen generated together with the oxygen due to electrolysis of the water in the forming acid electrolyte, especially towards the end of the process.  
      The hydrogen that develops not only entrains acid mists that are hazardous to health, in combination with the oxygen in the air above a certain concentration it can generate detonating mixtures.  
      This poses safety problems that make it necessary to adopt fume extraction and abatement systems, the size of which would have to be adapted, in the case of accelerated forming processes, to dispose of the larger quantities of hydrogen and acid mist due to the higher forming current involved.  
      A known method for effectively dissipating the heat generated during the forming process involves circulating the diluted forming electrolyte through a pipe from an outside tank to the battery and vice versa, so that the electrolyte can be cooled and its increase in concentration corrected by further diluting it with water to the required concentration.  
      Using this sort of method, an acid at the concentration needed for the battery&#39;s operation is added at the end of the forming process, thereby achieving a continuous “two-acids” process that ultimately produces finished batteries charged and ready for use.  
      Such a forming process with two acids in circulation is described in the Swedish Patent application SE-7701184-9- Publication No. 441403, submitted by the YUASA company.  
      This document fails to mention the safety problem posed by the hydrogen generated during the forming process.  
      The first aim of the present invention is to design a forming process with two acids in circulation in which the hydrogen and the related acid mists are disposed of in conditions of total safety.  
      Since ideal forming conditions, especially for the positive plate, demand a temperature between 40 and 60° C., it is important to ensure that the electrolyte is kept constantly at the right temperature throughout the forming process, and not just cooled.  
      The second aim of the present invention is consequently to develop a system for circulating the forming electrolyte in which not only its concentration, but also its temperature are kept stable at a given setting.  
      Moreover, it is desirable for the forming electrolyte to always be freshly prepared, so as to avoid any build-up of impurities that may derive from its repeated use in successive formations.  
      So, another aim of the present invention is to provide a system that enables the diluted electrolyte used in the first forming process to be used to prepare the more concentrated working electrolyte used for the second charge, which remains inside the battery, so that each finished battery, charged and ready for use, contains its “own” forming electrolyte.  
      When the battery is in use, i.e. when it is being discharged, the sulfuric acid in the electrolyte is “fixed” by the positive and negative plates in the form of lead sulfate, with a consequent progressive reduction in the concentration of the electrolyte.  
      If the active masses of the plates are oversized with respect to the amount of sulfuric acid in the battery, discharging can continue until the concentration of the electrolyte becomes similar to that of water.  
      In these conditions, the solubility of the lead sulfate in the plates increases, so it dissolves in the electrolyte, albeit in small quantities.  
      During subsequent recharging, the lead sulfate precipitates again because its solubility diminishes due to the increasing concentration of the electrolyte.  
      The lead sulfate that consequently builds up on the microporous separator, placed between the positive and negative plates to ensure their electrical insulation, is converted into metallic lead during charging.  
      This makes the separator electronically conductive, so it short-circuits the plates of opposite polarity and the battery becomes useless.  
      This risk exists particularly in modern starter batteries, where the amount of electrolyte, and consequently of sulfuric acid, is stoichiometrically inadequate for the quantities of the plates&#39; active masses.  
      To overcome this problem, it is common practice to include certain additives in the battery&#39;s electrolyte.  
      These additives are mainly soluble alkaline sulfates, that reduce the solubility of the lead sulfate when the electrolyte is very diluted.  
      The additive naturally represents an additional cost, as does the procedure required for its dosage.  
      Another aim of the present invention is therefore to provide a method for the automatic in situ production and dosage of additives for the electrolyte used in the forming process, starting from inexpensive raw materials.  
      Another important aim of the invention is to speed up the process of starter battery forming using two acids in circulation, optimizing the batteries&#39; performance, reducing the cost of the process and complying with environmental and safety requirements.  
      The above-specified aims, and others that will be better illustrated in the following pages, are achieved by a method for forming lead-acid batteries that, as stated in the first claim, is characterized in that it includes the following stages: 
          a first electrolyte, comprising a water solution of sulfuric acid at a given concentration and at an essentially constant preset temperature is drawn from a first tank through at least one first pipe;     said first electrolyte is distributed to one or more batteries by means of one ore more distributors complete with distribution channels, each of them connected to each of said batteries;     said first electrolyte is circulated continuously inside said batteries at a predetermined and substantially constant concentration and temperature for a given time, said first electrolyte entering and exiting through openings provided in said batteries, or battery cells, and returning to said first tank, level-detector devices having been provided to ensure a constant level inside each battery during said circulation;     said batteries are powered with a direct current while said first electrolyte is circulating for a given forming time;     the circulation of said first electrolyte from said first tank to said batteries is stopped and     a second electrolyte, kept at a predetermined and substantially constant concentration and temperature, collected from a second tank and comprising a solution of sulfuric acid and water, the concentration of which is always different from that of the first electrolyte, is then circulated in said batteries, or battery cells, for a further preset time;     said batteries are powered with a direct current while said second electrolyte is circulating for a preset mixing charge time.        

      One of the advantages of the method described in this invention is that, while the first electrolyte, comprising a water solution of sulfuric acid at a lower concentration than that of the second electrolyte, is circulating, it is kept at a constant concentration and temperature throughout the battery forming time.  
      Since it is common knowledge that the electrochemical reaction occurring inside the battery during forming involves the production of heat, the temperature of the circulating electrolyte tends to rise and its concentration obviously changes.  
      The fact that the method in this invention includes keeping the first electrolyte at a constant concentration and temperature while it is in circulation offers an obvious advantage in that the intensity of the current can be kept higher, throughout the forming process with the first electrolyte, than when the known technique is used, the known technique having to keep the current lower to avoid harmful overheating phenomena in the battery and the deterioration of the plates being formed.  
      The same applies to the second circulation with the second electrolyte, which is a water solution of sulfuric acid in a greater concentration than in the first electrolyte.  
      Here again, the temperature and concentration of the circulating electrolyte are kept constant, at a preset value, throughout the time it takes to perform the second mixing charge.  
      In essence, the constant temperature of the electrolyte on the one hand enables a faster forming process because higher charging currents can be used, since the heat generated is dissipated by cooling the electrolyte; on the other hand, a substantially identical forming of each battery, and a consequently similar performance of the batteries, is assured by the constant concentration of the electrolyte in both the first forming stage and the second mixing charge stage, thanks to a continuous re-titering of the electrolyte.  
      Moreover, the more diluted electrolyte used in the first forming charge is prepared by diluting with water the more concentrated electrolyte needed for the second mixing charge, which is drawn from the second storage tank, so that the mixing electrolyte is continuously being used up to prepare the first, more diluted electrolyte used for the initial forming charge, thereby avoiding the accumulation of the second electrolyte in its storage tank and ensuring its continual renewal.  
      The more concentrated electrolyte is also prepared by diluting with water an even more concentrated electrolyte, typically but not necessarily coinciding with the one used in the active mass production processes.  
      This particular, more concentrated electrolyte is treated with alkaline hydroxide additives in quantities sufficient to partially neutralize its sulfuric acid content in order to produce alkaline sulfates that will consequently be contained in the battery, at the end of the forming process, in the concentration needed to suppress the lead sulfate&#39;s solubility, so as to protect the battery against the risk of short circuits in the event it undergoes deep discharges.  
      The invention also concerns the plant for implementing the above-illustrated battery forming method. 
    
    
      Further characteristics and features of the invention behind the described forming method will become apparent in the description of a preferred form of implementation of the method object of the invention, given only as an illustrative and not restrictive example, and illustrated in the attached drawings, wherein:  
       FIG. 1  shows a layout of the plant for circulating the first electrolyte according to the method of this invention;  
       FIG. 2  shows the layout of the plant in  FIG. 1  when the second electrolyte, which is more concentrated than the first, is circulated;  
       FIG. 3  shows a schematic view of the connections between the batteries and the battery forming plant 
    
    
      Table 1 gives an example of the forming process carried out according to the method of the present invention, showing the process parameters and the performance of the batteries formed using said parameters.  
      With reference to  FIG. 1  and  FIG. 3 , a bench, indicated as a whole by 1, is used to support a number of batteries  2  that need to undergo the forming process.  
      Each of said batteries  2  has at least one positive pole terminal  210  and at least one negative pole terminal  220  that are connected to the forming plant&#39;s busbars for the delivery of a direct current  
      There is also a hole  230  where a plug  240  of known type is inserted, complete with a self-leveling device with two conduits, one for the delivery and one for the return of the circulating electrolyte.  
      All the batteries are connected in series, the positive and negative terminals in series being attached by means of connectors to two busbars, one positive and one negative, for carrying the direct electrical current  
      The electrolyte is delivered to each battery through a delivery pipe  310  connected to the distributor pipe  3 , while the electrolyte returns through a return pipe  410  connected to the collector pipe  4 .  
      The distributor pipe  3  and the collector pipe  4  are connected to the tanks  5  and  6  containing the electrolytes  7  and  8 , respectively.  
      To be more precise, the distributor pipe  3  is connected to the feed piping  9  and  13  when the circulating electrolyte is the electrolyte  7  contained in the tank  5 , or to the feed piping  10  and  101  when the circulating electrolyte is the electrolyte  8  contained in the tank  6 .  
      As for the collector pipe  4 , this is connected to the piping  12  or  11 , depending on whether the circulating electrolyte is the first electrolyte  7  or the second electrolyte  8 .  
      During the first stage of the process for forming the battery  2 , the first electrolyte  7 , consisting of a water solution of sulfuric acid at a certain concentration lower than that of the second electrolyte  8 , is collected from the first tank  5  and, through the valve  15  and the piping  13 , and with the aid of the pump  14 , it reaches the distributor pipe  3 , from where it is distributed through the delivery tubes  310  to each battery.  
      The electrolyte  7  is kept circulating by means of the fan  17 , which creates a negative pressure in the tank  5  and  6  because its intake is connected to the piping  171  which is in communication with the two tanks.  
      Since the tanks  5  and  6  are in communication with the collector pipe  4 , the negative pressure created by the electric fan  17  ensures a constant and continual intake of the electrolyte by the batteries being formed.  
      Each of the batteries  2  is fitted with a leveling device of known type that enables the electrolyte being fed to the batteries to reach a certain level L and not to exceed said level for all the time during which the electrolyte is in circulation.  
      In each battery  2 , the first electrolyte  7  reaches the level L, then exits through the pipe  4  and enters the liquid-gas separator  19  through the valve  18  and the piping  12 .  
      The liquid phase collects on the bottom of the separator and, through the piping  191 , reaches the bottom of the first tank  5 .  
      The gaseous phase, which contains hydrogen, is drawn off through the piping  192  at the top of the separator and arrives to the top of the first tank  5 , from where the it is extracted by the electric fan  17  through the piping  171 .  
      This first circulation continues for a preset time, during which the batteries are charged with a given current  
      As mentioned earlier, the electrochemical phenomena occurring inside the batteries  2  during the charge produce an increase in the temperature of the electrolyte  7 .  
      A temperature sensor  20 , situated in the piping  9  that delivers the electrolyte  7 , picks up the signal relating to the temperature of the electrolyte  7 . This sensor is connected to the heat exchanger  21 , which is enabled when the sensor  20  records a temperature variation with respect to a preset value, thus providing the cooling or heating capacity needed to restore the electrolyte  7  to the required temperature.  
      The electrolyte  7  is also kept at a constant preset concentration, controlled by means of a density meter  22  placed in the tank  5 .  
      The sulfuric acid generated during the plate forming process increases the concentration and consequently also the density of the electrolyte  7 , which thus departs from the established setting.  
      Demineralized water is consequently delivered to the first tank  5  through the pipe  23  from the tank  24  by means of the pump  25  and the valve  26 , which opens for the time necessary to restore the correct concentration of the electrolyte  7 .  
      After completing the forming charge according to the established time settings and current conditions, during which time the first electrolyte  7  has circulated at the established temperature and concentration, the second electrolyte  8 , which is more concentrated than the first electrolyte  7 , begins to circulate.  
      For this purpose, as shown in  FIG. 2 , the valves  15  and  28  close to cut off the circulation of the first electrolyte  7 , and the valves  29  and  30  open on the tank  6  containing the second electrolyte  8 .  
      This electrolyte  8  is delivered to the batteries  2  by the pump  31 , and returns to the second tank  6  through the pipe  4  and the valve  32 , after liquid-gas separation in the separator  33 .  
      In this separator  33 , in the same way as in the separator  19 , the liquid is collected and returned to the tank  6  through the piping  331 , while the gas passes through the piping  332  and reaches the top of the tank  6 , from where it can be extracted by the fan  17  through the piping  171 .  
      Here again, the temperature and concentration of the second electrolyte  8  are measured respectively by the temperature sensor  34  situated on the delivery piping  10  and by the density meter  35 .  
      The temperature is corrected in the heat exchanger  36 , which is controlled by the signal sent out by the temperature sensor  34 .  
      In the case of our example, the exchanger  36  is distinct from the exchanger  21 .  
      In other plant design solutions, a single heat exchanger may be used for both the first and the second electrolyte.  
      The concentration is corrected by adding preferably demineralized water from the tank  24  to the tank  6 , through the valve  27  and the pump  25  controlled by the signal coming from the density meter  35 .  
      During this phase, called the mixing phase, the first electrolyte  7  contained in the batteries  2  is replaced by the second, more concentrated electrolyte  8 , that becomes mixed with the first electrolyte  7  to produce an electrolyte at the working concentration established for the battery.  
      To facilitate the achievement of the working concentration throughout the battery, the batteries continue to be charged during mixing, but at a lower current rating.  
      All the above operations are managed by a programming and control device that is not illustrated in the figure, such as a computer controlling a CPU. It is clear from the above description that the batteries being formed are submitted to a forced circulation of the two electrolytes  7  and  8 , each at controlled and constant temperature and concentration, throughout the forming charge and the mixing charge.  
      The process as described guarantees a homogeneous charging of all the batteries and consequently their constant performance levels.  
      Moreover, temperature control of the circulating electrolyte throughout the forming cycle enables higher forming currents to be used, with a consequent reduction in the forming times which can be reduced by as much as 75%.  
      The methods for preparing the electrolytes  7  and  8  at the required concentrations differ significantly.  
      The first, more diluted electrolyte  7  is obtained starting from the second electrolyte  8  and diluting it with demineralized water.  
      For this purpose, as we can see in  FIG. 1 , the pump  38  transfers the second electrolyte  8  from the tank  6  to the tank  5 , while the water for its dilution is collected from the tank  24  through the pump  25  and the valve  26 .  
      The process for preparing the first electrolyte  7  is governed by the density meter  22 .  
      The second electrolyte  8  in the tank  6 , which is more concentrated than the first electrolyte  7 , is prepared in the second tank  6  starting from a third electrolyte  39 , more concentrated than either  8  or  7 , contained in a third tank  37 , from where it is sent to the tank  6  by the pump  43 .  
      The water for diluting the electrolyte is drawn from the tank  24 .  
      This demineralized water reaches the tank  6  via the pump  25  and the valve  27  and the process for preparing the second electrolyte  8  is governed by the density meter  35 .  
      As already mentioned, it is useful for the battery&#39;s electrolyte to contain salts, mainly soluble sulfates, to prevent the onset of short circuits in the battery when it is recharged after being deeply discharged.  
      The method of this invention consequently includes adding these soluble sulfates to the electrolyte  8 .  
      For this purpose, the alkaline hydroxide contained in a fourth tank  40  is drawn off by the pump  41  and added to the tank  37  before the third electrolyte  39  flows into the second tank  6  through the piping  16 , where it is diluted to produce the second electrolyte  8 .  
      The amount of alkaline hydroxide added to the sulfuric acid is controlled by measuring the density of the electrolyte in the tank  37  using the density meter  42 .  
      The gaseous phase extracted by the fan  17  contains hydrogen below its explosion threshold in air because it is diluted in each of the pipes  410  connected to the collector pipe  4 , each of which has an opening  44  that allows for the intake of sufficient volumes of air.  
      The concentration of the hydrogen is recorded at the inlet to the piping  171  using a known device  170 .  
      If the maximum allowable value for the concentration of hydrogen in the gaseous phase extracted by the fan  17  is exceeded, the charging process is automatically stopped, and the same applies in the event of any failure of the fan  17 .  
                                                           Rated                   1 st         3 rd         battery                   discharge   2 nd     discharge       capacity                   at C20   discharge at   at C20       C20   Forming   Time   Charge   Charge   factor   C20 factor   factor       (Ah)   method   (hours)   (Ah)   (Ah/kg m.a.+)   (% rated)   (% rated)   (% rated)                                                                62   Circulating   5   309   550   87   94   99           electrolyte       62   Conventional   20   309   550   90   95   99                  
 
      Table 1 compares the initial capacities of two idential starter batteries formed respectively by circulating the electrolyte according to the method described above and using a conventional system.  
      For the same amount of energy delivered during the forming cycle, the batteries demonstrate equivalent initial performance levels, based on their 20-hour capacity after being discharged three times, but the forming time using the circulating electrolyte method amount to 5 hours, i.e. a quarter of the time needed for conventional forming.  
      Clearly, therefore, all the specified aims have been achieved by the forming method object of the invention.  
      In particular, it is worth emphasizing that forming the batteries while the two acids are kept at constant concentration and temperature all the time the acids are circulating not only reduces the forming time, but also achieves a substantially constant quality of the batteries, which all feature the same charge and the same chemical transformation of the cells comprising each battery.