Lead battery and method for its manufacturing

FIELD: electricity.

SUBSTANCE: invention is attributed to lead batteries (AB). In this invention lead AB contains group of plates fitted into accumulator jar and ionogen introduced in it for plate group saturating with ionogen with simultaneous forming processing. Here lead AB is adapted to be used partly charged when charge condition is limited within interval from exceeding 70% to less than 100%. Plate group is formed by package consisting of large number of negative electrode bases including grid bases filled with active material of negative electrodes, of large number of positive electrode bases including grid bases filled with active material of positive electrodes and porous separator located between negative electrode bases and positive electrode bases. Ionogen contains at least one kind of ions selected from group consisting of aluminium ions, selenium ions and titanium ions.

EFFECT: creation of lead battery suitable to be used in partly charged condition.

23 cl, 9 tbl, 71 ex

 

The technical field

[0001] This invention relates to a lead battery and method of manufacturing of lead batteries. In particular, this invention relates to automobile lead battery, which can be used in partial state of charge (hereinafter referred to as SCS), as, for example, in the case of mode control charge or idling (idling-stop), and to a method of manufacturing such a lead battery.

Prior art

[0002] Typically, automobile lead battery is used as power supply when the actuation of the starter motor to start the engine, as the power source for lighting or ignition, or as the power source for the electric motors of various types, which can be installed in quantities of 100 or more in the case of the automobile high-class.

[0003] However, since the automobile lead battery is used so that the lead-acid battery is always powered by the actuation of the generator motor vehicle, except when to start the vehicle is driven by the starter up to the present time had m the hundred things, that car lead battery is not discharged so deeply. On the contrary, because of the lead battery is constantly in a state of overcharge, in most cases due to the charging motor generator, it is usually required that the lead battery has a high resistance to recharge. In addition, it is required that the lead storage battery has been designed in such a way that could have prevented the decrease of the electrolyte due to the formation of gas during charging, so that it doesn't require refilling water and maintained operation of the battery without significant maintenance. Taking into account the above, as the alloy for the positive electrode in the present instead of the alloy-type Pb-Sb use alloy type Pb-Ca.

[0004] However, because in recent years significantly increased requirements regarding the reduction of fuel consumption and minimize emissions of harmful exhaust gases of cars, the conditions of functioning of automobile lead battery has significantly changed.

[0005] One example of such conditions is to control the charge, i.e. the containment of charging the lead storage battery. Usually the car charging the lead battery is performed during operation of the generator, driven by the engine, as in the case of electricity supply to other electrical equipment. Therefore, the lead battery is always in a state of overcharge, which naturally leads to increased fuel consumption. In this regard, in the present control charge a lead battery, therefore reducing fuel consumption and minimizing the emissions of harmful exhaust gases.

[0006] in Addition, taking into account the reduction of fuel consumption by preventing overcharging of the lead battery is also proposed to detect the condition, which requires charging of lead batteries, and recharge lead batteries only in the case when this condition is detected, thereby avoiding excessive charging and reducing fuel consumption.

[0007] However, if the charging of lead batteries is performed only when it is found that recharging is necessary, on the basis of the detection result of the above partial state of charge (SCS) or the efficiency of fuel consumption, the ability to perform charging of lead batteries is limited, so that the lead battery will always be in SCS. However, if the lead and cumulativa battery is used in such a state of partial charge, the lead storage battery, particularly a lead battery, which has a low charging efficiency, will, on the contrary, the chronic lack of charging. In this case, you may need to run often so-called regenerative charging, in which the state of charge (hereinafter referred to as Sz) lead of the battery increases up to 100%to get out of the above state of chronic insufficient charging. As a consequence, fuel consumption, on the contrary, increases.

[0008] Another example of such operating conditions when using the lead battery is functioning, followed by the so-called regime "idling"at which the engine is "off" (suspended) while stopped due to the stop signal, etc. In this mode idle power from the generator power is also suspended due to the suspension of the engine. The result is that the power supply in this period of time will be provided by the discharge of lead batteries, consequently increasing the likelihood of discharge of lead batteries compared to normal battery operation, which also leads to the use of the battery VSCs. In this case also requires frequent execution of the so-called regenerative charging of lead batteries, which leads to increased fuel consumption.

[0009] the State of charge of a lead battery in this SCS usually limited to the range from 70% to less than 100%. As in the case of the car where the engine start is guaranteed through the use of only one lead of the battery, in principle there is the possibility of problems with starting the engine, if Sz is not more than 70%. Therefore, the lower limit of the Sz usually set large 70%.

[0010] on the other hand, 100%state of charge cannot be achieved if only the lead battery is constantly recharged with the transition into a state of overcharge. However, this recharge would increase fuel consumption, as described above. Therefore, the upper limit of the Sz is usually set lower than 100%.

[0011] in Addition, in the case of the hybrid system (HVS), in which electricity when braking in generator mode is stored temporarily in the lead battery and then quickly given with the assistance of an acceleration, even if the lead battery must operate in a state of partial charge, as described above, the lead accumulator is of atarea usually operates at the upper limit state of charge of not more than 70%, to ensure high efficiency charging. Lead storage battery according to the prior art, which has a hybrid function, in which the regenerated electric power is used for charging and discharging of lead batteries, described in a publication published patent applications in Japan (Kokai) No. 2003-36882 and publishing published patent applications in Japan (Kokai) No. 2003-51334. In accordance with these publications NW always limited intervals of 50-70% in order to perform quick charging and high efficiency. In this case, however, separately installing the battery to start the engine in order to resolve any issues in relation to engine start at low temperatures.

[0012] In the case where the charge control or idling perform under this condition with the use of conventional lead batteries, which are designed taking into account the importance of the corrosion resistance of a lattice of positive electrode plates or General corrosion when recharging, it is impossible to ensure sufficient efficiency charging, despite the fact that opportunities for charging, not so much. Consequently, the conventional lead battery prone to drift into a state of chronic insufficient charging. If this problem should bitratrate, requires frequent recovery charge, which makes it impossible for a sufficient helping to reduce fuel consumption, which is essentially directed control of a charge.

[0013] in Addition, after the conventional lead storage battery is provided in a state of chronic insufficient charging, in which the lead storage battery is maintained in a state of partial charge, not only the surface of the negative electrode, but also the surface of the positive electrode is exposed to the effect of sulfate crystallization, which accumulates the sulphate of lead, which creates the problem, expressed in a significant reduction of the service life of the lead storage battery.

[0014] due To this problem proposed flooded lead-acid batteries and sealed lead-acid batteries in which the electrolyte is added about 0.1 mol/l of sulfate of an alkali metal (such as sodium) or aluminum-sodium alum, which is a double salt consisting of sodium and aluminum, to prevent short circuit caused by the decrease of the density of the electrolyte due to the continuous discharge (publication laid patent application of Japan (Kokai) No. 8-64226 (1996)).

[0015] However, in the result of extensive research performed by avtora the present invention, it was found that, despite the fact that the above objective can be achieved in the case of conventional lead batteries used in a fully charged state, is difficult in the case of lead batteries, which are designed for use in SCS, the charging efficiency which significantly deteriorates due to the influence of sodium ions, which has a significant negative impact on the achievement of the above goals.

[0016] as a means of overcoming sulfate crystallization of the negative electrode lead of the battery is known for the idea of adding in the negative electrode carbon in larger quantities compared to it is usually used by a number of Journal. Power Sources, vol. 59(1996), 153-157). Although in this earlier publication says nothing about the amount of added carbon, it is described that added so carbon has the possibility of introducing into the voids of sulphate of lead with the formation thereby pathway. Therefore, the author of the present invention have performed various tests, which have experienced a wide range of values of carbon. In the result, it was found that the effects of increasing the service life of the lead battery is limited in terms of control of charge or idle stroke is and what the industry perspective is difficult practical use of this idea when monitoring charge or idle mode.

[0017] it is also Known preceding technical solution, in which the electrolyte add organic acid, such as polyacrylic acid, or ester (Publication laid patent application of Japan (Kokai) No. 2001-313064). However, this prior solution has the disadvantage that the grid plate is subjected to corrosion, and it is not suitable for practical use. In addition, it is also known preceding technical solution, in which the gel electrolyte add titanium, aluminum or potassium to improve the efficiency of running at low temperature (publication laid patent application of Japan (Kokai) No. 60-211777 (1985)). However, the technology described in the preceding technical solution, has the tendency to deterioration of the electrical conductivity of the electrolyte and is not able to provide the claimed improvement. In addition, it is also known preceding technical solution, in which the electrolyte add selenium and organic acid to suppress the formation of hydrogen at the negative electrode, and help to reduce the amount of oxygen (Publication laid patent application of Japan (Kokai) No. 64-38970 (1989)). However, in accordance with these preceding technical solution, the amount of added selenium great and is 100-1000 ppm, which causes the no deposition of selenium from the electrolyte, which, on the contrary, a negative effect on the lead-in battery.

[0018] Another reason for the reduction of the service life of the lead battery can be that due to the requirement to develop a maintenance-free lead batteries the base material of the positive plates of lead batteries changed with material type Pb-Sb material type Pb-Ca. In the case of the commonly used alloy Pb-Sb pentavalent antimony ions, which are formed during the oxidation bases of the plates have the ability to impact on the active material in such a way that increase the adhesion at the interface between the active material-grid plate, thereby transforming the portion of the active material in the gel to harden linking with the rest of the active material. As a result, even if deep charge/discharge is repeated, it can prevent peeling of the active material from the grid plate or softening of the active material.

[0019] However, in the case of alloy-type Pb-Ca, the above effect can be achieved through antimony, significantly weakened. Therefore, when the repetition of deep charge/discharge of the active material begins to pull away from checker plates at an early stage, binding in the active material deteriorates and, accordingly, the active material of the size of goalsa, that reduces the battery life.

[0020] the Author of the present invention has been proposed alloy for the base electrodes of lead batteries (publication laid patent application of Japan (Kokai) No. 2003-306733), which provides the possibility of increasing the corrosion resistance and the mechanical strength of the electrode plates, and this alloy contains 0.02 to 0.05 wt.% Ca, 0.4 to 2.5 wt.% Sn of 0.005 to 0.04 wt.% Al and 0,002-of 0.014 wt.% Ba. This alloy may further contain at least one kind of element selected from the group consisting of 0.005 to 0.07 wt.% Ag, 0.01 to 0.10 wt.% Bi and 0.001 to 0.05 wt.% That.

[0021] However, it was found that even in the case of this high corrosion resistance alloy for the base electrode characteristics such as adhesion between the positive electrode and the active material and the strength of the links in the active material is much worse compared with the conventional alloy-type Pb-Ca, which creates problems in these aspects.

[0022] Believe that calcium ions by their nature, have the ability to improve adhesion between the lattice plate and the active material or the adhesion of the active material (Journal. Power Sources, vol. 64(1997), 51-56). Undoubtedly, it was found that such a function have calcium ions, which are washed away from the base plate composed of an alloy containing 0.06 to 0.1 wt.% of calcium.

[0023] on the other hand, believe that the persistence of this alloy to corrosion tends to increase at lower Ca content in this alloy. In the case of the alloy for the base of the plates disclosed in the above publication laid patent application of Japan (Kokai) No. 2003-306733, for example, the resistance of this alloy to corrosion was significantly increased when the content of Ca was less than 0.05 wt.%. In contrast, however, it was found that this alloy intake washed from an alloy of calcium ions to the active material decreases, making it difficult to improve the adhesion of the active material.

[0024] Also, there is a method that aims at overcoming the above problem, in which on the substrate surface of the positive electrode precipitated layer containing antimony, or to the base type compound of antimony, resulting receive the same effects as in the case of alloy-type Pb-Sb (publications published patent applications in Japan (Kokai) No. 49-71429 (1974); No. 53-75444 and No. 63-148556).

[0025] in Addition, there are various ways that help maintain the same strength of ties the active material, which can be obtained from the use of antimony; such preceding technical solution include a method in which the surface layer of the basis electrode formed by a layer of lead alloy containing at least one element selected from alkali metals and alkaline earth metals (WO-01/04976-A1); a method in which the layer of active material introduced dioxide, tin and calcium sulfate (publication laid patent application of Japan (Kokai) No. 9-289020 (1997)); and the way in which the active material of positive electrodes introduced 0.5 to 5 wt.% (calculated as metallic tin, and the mass of the active material of positive electrodes) of the metallic tin or tin compounds, and at the same time, the density of the active material of positive electrodes is in the range of 3.8-5.0 g/cm3(publication laid patent application of Japan (Kokai) No. 10-188963 (1998)). All these preceding technical solution, naturally, is effective in conditions where there may be used conventional lead battery.

[0026] However, under such conditions of use, when the lead storage battery is controlled by charge or idle mode, due to the fact that the charging/discharging is repeated in SCS for a long period of time, the above countermeasures are ineffective for resolving problems with shedding or softening of the active material.

[0027] furthermore, in addition to the requirements of the lead battery in reducing fuel consumption and reduce exhaust emissions, you must also improve the performance of the run (the ability to discharge) and the active material of positive electrodes, making it possible to reduce the weight of the battery. For improved active material of Politechnicheskaya lead batteries attempts were made to improve the distribution of the electrolyte. For this purpose usually use a method of reducing the density of the porous active material of positive electrodes.

[0028] However, when using alloy type Pb-Ca as lattice plates of the positive electrode active material tends to peel from the lattice plates due to charging/discharging, and, in addition, this active material is subject to softening and shedding, resulting in significantly reduced battery life. To resolve the above problems, a method for introducing a graphite active material of positive electrodes.

[0029] In this case, the graphite expands as sulfate ions intercalibrate in voids due to the introduction of the electrolyte, respectively, forming voids in the active material, these voids in the active material further increases as a result of diffusion during oxidation during charging. However, the expansion of graphite causes at the same time the destruction of the active material, thereby also reduces battery life. Consequently, the above method applies only to the lead battery is a sealed type, in which a group of plates is strongly compressed. However, even in this case, it may be deformation or destruction of the battery banks due to the extended positive electrode.

[0030] a is Yu overcome the above problems was proposed method, in which the powder of lead, minium, fibrous resin, expanding graphite and dilute sulfuric acid are mixed under reduced pressure to form a paste, which is used for manufacturing the active material (publication laid patent application of Japan (Kokai) No. 2004-55309). Although all of these preceding technical solutions undoubtedly effective under conditions where the lead battery is used in the usual manner, the above-mentioned preceding technical solutions are not effective enough in those conditions when the lead storage battery is controlled by charge or idle mode, due to the fact that the charging/discharging is repeated in SCS for a long period of time.

Disclosure of invention

[0031] the present invention is to provide an automobile lead battery, which is adapted for use in conditions where its charging/discharging is repeated in a state of partial charge (SCS), as, for example, in the case of control of charge or idle mode, and this lead rechargeable battery capable of providing a significant improvement in the efficiency of charging under the conditions, when the state of charge is limited within the range from 70% to less than 100%.

[0032] For resinification tasks proposed lead storage battery in accordance with one embodiments of the present invention, which is characterized in that the electrolyte is introduced at least one type of ions selected from the group consisting of aluminum ions, selenium ions and titanium ions. Also offered in a lead storage battery in accordance with another embodiment of the present invention, which is characterized by the fact that the content of sodium ions in the electrolyte is limited by the interval of 0.002 to 0.05 mol/L.

[0033] In accordance with another aspect of the present invention a method of manufacture of lead storage batteries, containing a group of plates, placed in the battery Bank, and entered into the electrolyte for impregnation of the group of plates in the electrolyte to perform forming processing, and this lead rechargeable battery adapted for use in a state of partial charge, when the charge status is limited within the range from 70% to less than 100%, while the group of plates is formed by a package consisting of a large number of bases of the negative electrode that includes a lattice basis, filled with active material, a negative electrode, a large number of foundations of positive electrode comprising a lattice basis, filled with the active material of positive electrodes and a porous separator located between the bases of the negative e the W and positive electrodes; moreover, this method is characterized in that at least one kind of compound or metal that is soluble in an aqueous solution of sulfuric acid and contains aluminum ions, selenium ions or titanium ions injected into the active material of the positive electrode or placed in contact with the electrolyte on a plot of battery banks, thereby providing the possibility of leaching of these ions in the electrolyte with the formation of an electrolytic solution containing at least one kind of ions selected from the group consisting of aluminum ions, selenium ions, titanium ions and lithium ions.

The best option of carrying out the invention

[0034] the Present invention relates to a lead battery, which is adapted for use in a state of partial charge (SCS when the state of charge (Sz) limited within the range from 70% to less than 100%, and the electrolyte contains at least one kind of ions selected from the group consisting of aluminum ions, selenium ions or titanium ions. As for the content of these ions, the content of aluminum ions should be limited within the interval 0.01 to 0.3 mol/l, the content of selenium should be limited within the interval is 0.0002-0,0012 mol/l and the content of titanium ions should be limited within the interval of 0.001-0.1 mol/L.

[0035 If the content of aluminum ions is less than 0.01 mol/l, the effect of improving the charging efficiency becomes insufficient. On the other hand, if the content of aluminum exceeds 0.3 mol/l, the conductivity of the electrolyte decreases, resulting in worsening of the characteristics of the charging ability of the battery to a rapid discharge.

[0036] If the content of selenium ions less is 0.0002 mol/l, the effect becomes insufficient. On the other hand, if the content of selenium exceeds 0,0012 mol/l, selenium metal tends to be precipitated in the electrolyte, resulting in the apparent negative effect, namely, that precipitated selenium causes a short circuit, and, in addition, even if the content of selenium above the specified upper limit, it is impossible to expect any additional improve their effect. If the content of titanium is less than 0.001 mol/l, the effect becomes insufficient. On the other hand, if the content of titanium exceeds 0.1 mol/l, the conductivity of the electrolyte deteriorates, which affects the characteristics of the charging ability of the battery to a rapid discharge.

[0037] Since it was found that the presence of sodium ions in the electrolyte of the lead battery prevents the influence of aluminum ions to improve the efficiency of charging, it is the actual content of sodium ions is limited to the value not more than 0.05 mol/L. Although it is known that usually sodium ions and magnesium ions are added in accordance with increase in the concentration of sulfate ions in the electrolyte, the presence of sodium ions in the electrolyte affects the efficiency of charging a lead battery of the present invention. Although the reason for this is unclear, sodium ions in the electrolyte to act in such a way that degrade the charging efficiency in SCS, resulting in reduced effect of increasing the efficiency of the charge generated in the present invention by the use of aluminium ions, selenium ions and titanium ions. In addition, suppose that the sodium ions have other negative impacts, which are particularly evident at temperatures not exceeding the normal temperature at which the charging efficiency is degraded.

[0038] the Lower limit of the content of sodium ions is 0.002 mol/L. Even if this lower limit is additionally reduced, it is impossible to expect any additional benefits. In addition, since the lignin used as an additive to the negative electrode, is essentially sodium salt, in the case when the content of sodium ions is reduced below the above lower limit, it is, on the contrary, would lead to the reduction of the added lignin and thus the reduction of the service life of the lead item is Torno battery.

[0039] Publication laid patent application of Japan (Kokai) No. 2003-36882 describes a lead-in rechargeable battery that uses the regenerated energy in a state of partial charge (SCS) or charging status 70-100% and in which the negative electrode is added the specified number of carbon, barium sulfate or lignin and electrolyte added at least one kind of material selected from K, Ca and Al. However, the document does not say anything about the negative effects of sodium. In addition, the publication published patent applications in Japan (Kokai) No. 2003-51334 disclosed the idea of adding to the electrolyte is at least one kind of material selected from K, Ca and Al, in a predetermined ratio in order to prevent the deterioration of the negative electrode due to their sulfate crystallization. This document says nothing about the negative effects of sodium on the lead-in rechargeable battery that uses the regenerated electricity in SCS or charging status 70-100%.

[0040] At the same time, the present invention is directed to a lead battery, which is adapted for use in SCS, when the state of charge is limited within the range from 70% to less than 100%, and which is designed for repeated use for a long time when Adebola deep charge/discharge. Therefore, to improve the efficiency of charging the content of sodium ions in the electrolyte must be limited to a value of 0.05 mol/l or less. In addition, the author of the present invention it was discovered that by adding to the electrolyte is at least one kind of ions selected from ions of aluminum, selenium ions and titanium ions, in an amount of 0.01 to 0.3 mol/l of aluminum ions, is 0.0002-0,0012 mol/l for selenium ions and 0.001-0.1 mol/l titanium ions may improve the efficiency of battery charging.

[0041] the Lead storage battery in accordance with the present invention is characterized by the fact that her plate is formed from an alloy based on lead-calcium containing 0,02-0,05 wt.% Ca, 0.4 to 2.5 wt.% Sn of 0.005 to 0.04 wt.% Al, 0,002-of 0.014 wt.% Ba, the rest lead and unavoidable impurities.

[0042] Ca contributes to increasing the mechanical strength of the plates. If the Ca content is less than 0.02 wt.%, the mechanical strength of the plate becomes insufficient, and if the Ca content exceeds 0.05 wt.%, it deteriorates the stability of the plates to corrosion. When the Ca content is limited to the above interval and the Ba content is limited to the interval of 0.002-of 0.014 wt.%, it is possible to improve the resistance of the plates to corrosion while enhancing their mechanical strength. If the Ba content is less than 0.002 wt.%, the mechanical strength of the plates with enevitsa insufficient, and if the Ba content exceeds of 0.014 wt.%, it deteriorates the stability of the plates to corrosion. The addition of tin increases fluidity of the molten alloy and the mechanical strength, and at the same time, checker plates of lead batteries, as well as the surface of the partition lattice-based active material may be doped with tin, resulting in increased conductivity. If the content of tin is less than 0.4 wt.%, the above effects become negligible, and along with it is the lack of stability of plates to corrosion. In addition, if the tin content exceeds 2.5 wt.%, the crystal grain plates become more rough, which causes the occurrence of corrosion at grain boundaries with higher speed as compared with visible corrosion. Add Al helps curb losses of Ca and Ba, which can be caused by oxidation of the melt, and the Al content is limited to a value not more than 0.04 wt.%. If the aluminum content exceeds 0,04 wt.%, the aluminum has a tendency to selection in the form of dross.

[0043] When at least one kind of metal and/or compounds of a metal selected from bismuth, antimony and calcium included in the base surface of the positive electrode or the active material of positive electrodes of the present invention, this is effective to improve the adhesion between the active material of the positive electrode and the surface of the partition lattice plate or in the active material. The base surface of the positive electrode active material of the positive electrode may also contain tin and/or arsenic in the form of metal or compounds to further improve adhesion.

[0044] Although the cause of those effects that can be achieved using tin or arsenic, is still not precisely determined, they, apparently, can be attributed to the phenomenon that the layer α-PbO2i.e. the boundary surface between the base and the active material, legarrette tin, and, thereby, increases the conductivity of this layer, providing the possibility of manifestations of essentially the same effects as those, which increases adhesion on the surface of the partition. Mainly because there is a message that, when doped PbO2bismuth its catalytic ability to oxidation can be improved, it is assumed that the tin contributes to the stabilization of SnO2having a high electrical conductivity. Regarding the adhesion of the active material is also possible that, although its surface, which reacts with an aqueous solution of sulfuric acid, forming the electrolyte, formed from β-PbO2the inner portion of the active material formed from the α-PbO2so that will be achieved virtually the same effect.

[0045] Although arsenic compared with tin worse to have the tion of the effect of improving conductivity, however, in the case of its use can also be made the effect of increasing the conductivity, and simultaneously arsenic helps curb the dissolution of antimony and the prevention of the deterioration of the hydrogen overvoltage of the negative electrodes. Therefore, arsenic is suitable to improve performance maintenance-free batteries.

[0046] As described above, the effect of prolonging the service life of the lead battery through the use of bismuth, antimony, calcium, tin and arsenic was previously known. However, this known technology is limited to the situation when the active material is in a state of PbO2i.e. in the charged state, which is completely different from those circumstances in which the lead storage battery operates in an idle mode or control charge, when simultaneously present, the sulphate of lead, and the battery is constantly under conditions of incomplete charging.

[0047] In particular, it is important that the lead sulfate formed under conditions of incomplete charging, as in the case of idling or control charge, reversible can be oxidized to PbO2when charging, by providing the ability to properly frame the structure of the active material. If the sulphate of lead is always the opportunity to stay n is reversible even when charging, the skeleton of the active material is gradually destroyed, resulting in softening of the active material.

[0048] At the same time, it is assumed that the aluminum ions, selenium ions or titanium ions included in the electrolyte in accordance with the present invention are capable of preventing the above-mentioned undesirable effect in the lead battery, which is used in idle mode or control of a charge.

[0049] namely, since the electrolyte of lead batteries, located in a state where NW corresponds to 70% or more, has a relatively high density, solubility of lead sulfate is reduced. However, when added to the electrolyte ions of aluminum, etc. these additives adsorbed ions Pb2+thereby complementing ions Pb2+the disadvantage which may occur during charging. As a result, assumed to be inhibited polarization, which leads to improvement of the efficiency of charging.

[0050] in Other words, due to the reaction of dissolution/precipitation during charging, the following reactions occur: PbSO4→PbO2on the positive electrode; and PbSO4→ Pb on the negative electrode. In this case, if the concentration of sulfuric acid in the electrolyte is high, and its density is high (when the NW pillar is t not less than 70%), solubility PbSO4becomes low and the dissolution of ions Pb2+decreases, thereby decreasing their concentration and deteriorates the charging efficiency. However, if there are ions of Al and the like, it is assumed that ions Pb2+available around the Al ions will be adsorbed and captured Al ions, thereby increasing the concentration of ions Pb2+. The result can be facilitated oxidation and reduction of ions Pb2+that increases the charging efficiency.

[0051] As described above, due to the influence of bismuth, antimony and calcium with the addition of tin or arsenic possible inhibition of exfoliation of the active material from the grid plates or softening of the active material. In addition, the result of the action of aluminium ions, selenium ions or titanium ions simultaneous improvement in the reversibility of lead sulfate formed in the positive and negative electrodes, which makes it possible to extend the service life of the lead battery is used under conditions of idling or control recharge. The extension of the service life of such a lead battery can be achieved not only in terms of a mode of idling, etc. but under normal conditions of use.

[0052] as the method of introduction of bismuth, antimony and calcium with the addition of the ova or arsenic lead acid rechargeable battery can be used a method of mixing these substances with the active material or the method of application of these substances in the form of a layer on the surface of the base electrodes. Preferred primitively amount (calculated as metal) of these substances are 0.005-0.5 wt.% for bismuth; 0.005 to 0.2 wt.% for antimony; 0.05 to 1.5 wt.% for calcium; 0.005 to 1.0 wt.% for tin and 0.005-0.2 wt.% for arsenic. When primitively quantities of these substances is less than the above lower limit, it is impossible to ensure their actions. In addition, when primitively quantities of these substances more than the above upper limits, the expected effects will be worse in the case of bismuth, the ability to operate without maintenance will deteriorate in the case of antimony and anticipated effects will be worse in the case of calcium. In addition, in the case of tin add more than the upper limit does not cause any increased effect and at the same time could cause a short circuit due to dissolution in the electrolyte. In the case of arsenic add more than the upper limit leads to deterioration of the expected effects.

[0053] in Addition, adding the expanding graphite positive electrode lead rechargeable battery according to the present invention this expanding graphite is oxidized and disappears during charging, respectively, forming voids in the active material that allows you to use the inside of emptiness as the active surface relative to the ele is trolyte and therefore, allows the active material to exhibit a high coefficient of efficiency. As a consequence, will accelerate the softening of the active material. On the other hand, however, adding bismuth to the active material may doping bismuth β-PbO2that is an active material of positive electrodes, the water in the crystals β-PbO2stabilized and locally denaturised in the hydroxide of lead, which is known to inhibit the above-mentioned softening, because it serves as a glue between the particles of the active material.

[0054] namely, when the joint addition of the expanding graphite and bismuth in the active material of positive electrodes inside voids, which are formed due to the addition of the expanding graphite, will podselitsya, thereby creating the environment of the electrolyte, which can easily form a hydroxide of lead. Namely, the addition of bismuth in this case leads to improved deterrence effect of softening active material as compared with the effect obtained by the addition of bismuth in accordance with the prior art. In this case, since the electrolyte add the aluminum ions, selenium ions or titanium ions, these atoms have the possibility of introducing into the crystal lattice Sul the veil of lead, deforming its lattice, or have the ability adsorption on the crystal surface, preventing the growth of these crystals, resulting in inhibited growth of crystals of sulphate of lead. As a result, the reversibility of lead sulfate into lead can be improved, which makes it possible to further suppress sulfate crystallization.

[0055] Peremeshivaemogo number of expanding graphite should preferably be limited to the range of 0.1 to 2.0 wt.% in the calculation of the active material of positive electrodes. If peremeshivaemogo expanding the number of graphite is less than 0.1 wt.%, it is impossible the achievement of the expected effects from it. In addition, even if peremeshivaemogo number of expanding graphite exceeds 2.0 wt.%, it is impossible to expect any improved effects, and at the same time is difficult cooking pasta. Peremeshivaemogo amount of bismuth should preferably be limited to the interval of 0.01-0.5 wt.% (in terms of pure metal), based on the active material of positive electrodes. If peremeshivaemogo amount of bismuth is less than 0.01 wt.%, it is impossible the achievement of the expected effects from it. In addition, if peremeshivaemogo amount of bismuth exceed 0.5 wt.%, it is most likely that this will lead to a deterioration of the discharge characteristics.

[0056] in Addition, lead is the battery of the present invention can increase its capacity by adding to the electrolyte a small amount of lithium ions. Adding lithium ions to the electrolyte, the lithium ions can be introduced into the crystal lattice of the oxide of lead, violating its crystallinity, resulting in improved efficiency of the positive electrode. The content of lithium ions preferably should not exceed 0.14 mol/L. If lithium ions are added to the electrolyte in amounts exceeding this upper limit, on the contrary, the battery life will be reduced. To ensure the improvement of the efficiency of use of the positive electrodes, add enough of lithium ions in an amount not less than 0,005 mol/L.

[0057] In the lead-in rechargeable battery in which the electrolyte is included lithium ions, effects due to the addition of aluminum ions, selenium ions or titanium ions to the electrolyte, are the following. Namely, increasing the size of the crystals and compaction of the particles of sulphate of lead, which may be formed in the positive or negative electrode can be suppressed aluminium ions, selenium ions or titanium ions, allowing for the renewal of lithium to the maximum possible value. This may result in the reduction of weight of lead batteries, and at the same time extending battery life by improving the efficiency of IP is the use of positive electrodes.

[0058] it is common practice to add carbon to the negative electrodes as a means of preventing sulfate crystallization negative electrodes. In the present invention, however, the electrolyte is added at least one kind of ions selected from ions of aluminum, selenium ions and titanium ions, in addition to carbon. This may result in a significant improvement in the efficiency of charging of the negative electrodes in lead battery, which is designed for use in a state of partial charge. Although the reason for this is not clear, assume that the aluminum ions, selenium ions and titanium ions capable of increasing the concentration of sulfate ions on the surface of the negative electrode and also capable of suppressing the controlled diffusion of the electrolyte during charging. The amount of carbon peremeshivaemogo to the negative electrodes should preferably be limited to an interval of 0.05-5 wt.% in the calculation of the active material of the negative electrodes. If peremeshivaemogo the amount of carbon less than 0.05 wt.%, it is impossible the achievement of the expected effects from it. On the other hand, if peremeshivaemogo the amount of carbon exceeds 5 wt.%, during charging can be formed in a significant amount of hydrogen gas, so that the amount of electrolyte decreases rapidly, h is about is the increase in internal resistance.

[0059] In the present invention the aluminum ions, selenium ions or titanium ions, and lithium ions can be introduced into the electrolyte, which compounds or metals containing these elements and soluble in an aqueous solution of sulfuric acid, for example, add initially in the active material of positive electrodes, and then these ions allow to dissolve in the electrolyte from the positive electrode. If these compounds or metals add to the negative electrodes, ions can be trapped or restored to metals, especially in the case of selenium. It is therefore recommended to introduce these compounds or metals in the active material of positive electrodes. Alternatively, these compounds or metals can be placed on the section of the battery banks, where these compounds or metals may come into contact with the electrolyte, resulting in these compounds or metals can dissolve in the electrolyte.

EXAMPLES

(Examples 1-13; Comparative examples 1-7)

[0060] When using the composition of the alloy for the basics of the positive electrode, which consists of 0.04 wt.% calcium, 1.0 wt.% tin, of 0.015 wt.% aluminum 0,008 wt.% barium, the rest lead and unavoidable impurities, were made by cast basis using the die with a vertical connector of type "book". Casting was performed with a speed of 15 whether the LLC in a minute. Cast thus the foundations were subjected to heat treatment for 3 hours at a temperature of 120°C for the production of dispersion-strengthened foundations. Then these dispersion-strengthened fundamentals filled paste of active material of positive electrodes prepared with well-known conventional method. The resulting framework was combined with the negative plates of the electrodes prior to their formation (i.e. not subjected to formation), which were cooked well-known in the usual way, and with polyethylene separators. The resulting team of the workpiece placed in the battery Bank, which was introduced (injected) an electrolyte comprising a dilute aqueous solution of sulfuric acid, by performing the formation of the battery banks, the result produced lead battery 12V size D23, nominal capacity during 5-hour charge was 50 And·'clock This lead battery used as a lead battery in comparative example 1.

[0061] Then, similarly to the above method of manufacturing lead batteries were prepared electrolytes of different types when used in the form of sulfate, aluminum ions, selenium ions, or ions of titanium and different variations of these quantities. Atelectasia accordingly introduced into the battery banks with the implementation of the formation of the battery cans, making thus lead-acid batteries 12 In size D23, the rated capacity of which is at a 5-hour charge was 50 And·hours depending on the amount of these metal ions produced battery was attributed to lead rechargeable battery for the embodiments of the present invention and lead to the batteries of comparative examples 2-7. In the analysis of these electrolytes lead batteries that have been mentioned above formation, it was found that the concentration of sodium ions is in the range from 0.01 to 0.02 mol/L. the charging Efficiency of these lead batteries were evaluated as follows.

[0062] First of all, these lead-acid batteries fully charged at a temperature of 25°C with rated current for 5 hours. Then these lead-acid batteries were subjected to a cyclic test, which was repeated ten thousand times under conditions of idling. Namely, one cycle of this cyclic tests consisted of a period of the discharge direct current for 59 seconds at a current of 50 a and for one second at a current of 300 a at 40°C and period of charging with a constant current/constant voltage for 60 seconds at a current of 100 a and the upper limit voltage of 14.0 Century In the Le of this was accomplished discharge lead acid batteries at a temperature of 25° C with rated current for 5 hours, respectively evaluating the efficiency of charging the residual capacity to the initial capacity. The results are presented in table 1.

Example 5
Table 1

Types of added ions and the charging efficiency
Types and number of ions (mol/l)The proportion of the residual capacity
No.AlSeTi(%)
Comparative example 1---35
Comparative example 20,005--46
Example 10,01--56
Example 20,1--67
Example 30,3--53
Comparative example 30,4--45
Comparative example 4-0,0001-43
Example 4-is 0.0002-52
-0,0005-61
Example 6-0,0010-64
Example 7-0,0012-64
Comparative example 5-0,0015-Se, precipitated in the form of metal
Comparative example 6--0,000541
Example 8--0,00152
Example 9--0,0163
Example 10--0,155
Comparative example 7--0,248
Example 110,10,001-68
Example 120,1-0,0168
Example 130,10,0010,0169

[0063] As is clear from the results shown in table 1, in the case of the examples according to the present invention, in which the content of aluminum ions was limited to the interval from 0.01 to 3 mol/l, the content of selenium was limited to the interval is 0.0002-0,0012 mol/l or the content of titanium was limited to the interval of 0.001-0.1 mol/l, the percentage of residual capacity in any of these examples was 50% or more. In contrast, in the case examples in which aluminum ions, selenium ions or titanium ions were not included in the electrolyte or the content of these ions in the electrolyte beyond the above intervals, the percentage of residual capacity in all of these examples was less than 50% or more. In addition, as can be seen from examples 11 to 13, even if two or more types of ions selected from ions of aluminum, selenium ions and titanium ions were included in the electrolyte, it was possible to achieve a share of the residual capacity of 50% or more.

[0064] In these examples, the metal ions were added to the electrolyte in the form of sulphate. However, the present invention is not limited to the above sulfates. Namely, these ions can be added in the form of a metal or compound such as a sulfite, carbonate, bicarbonate, phosphate, borate, hydroxide, metallic salt of the acid, if the metal or the compound is soluble in an aqueous solution of sulfuric acid. In addition, in these examples, these metal ions were used in the battery by dissolving them in the electrolyte, followed by the introduction of the electrolyte in lead akkumulatorenwerke. However, these compounds, which are soluble in an aqueous solution of sulfuric acid, can be added to the active material of positive electrodes or are in contact with the electrolyte in the battery Bank, whereby there is the possibility of dissolving these compounds in the electrolyte with the formation of ions.

[0065] As aluminium and selenium soluble in sulfuric acid, they can be added or mixed in the form of small pieces or powder to the positive electrode or to be in contact with the electrolyte in the battery Bank, whereby there is the possibility of dissolving these compounds in the electrolyte with the formation of ions.

[0066] the Alloy used for the positive electrode may optionally contain, in addition to the above metals or compounds, at least one kind of element selected from silver, is added in amounts of 0.005 to 0.07 wt.%, bismuth is added in an amount of 0.01-0.10 wt.%, thallium added in amounts of 0.001 to 0.05 wt.%. In addition, although in these examples used a lattice basis, made by casting without application of pressure, the present invention surely can also use bases obtained by continuous casting or deformation processing by rolling. In addition, although the lead and the rechargeable batteries that are provided, used in these examples were performed as flooded lead-acid batteries, in which was placed a significant amount of free electrolyte, it was possible to achieve almost the same effect as that described above, even in the case of a sealed lead storage battery, which was fitted with a valve pressure control.

(Examples 14-17; Comparative examples 8 and 9)

[0067] in the same manner as described in example 1 were made of lead-acid batteries in which the electrolyte were included with the aluminum ions. However, in these examples, the number of sodium ions included in the electrolyte after the formation, consistent with the values presented in table 2. In the same manner as described in example 1, was evaluated these lead-acid batteries. The results are presented in table 2.

Table 2

The number of added ions and the charging efficiency
The amount of Al (mol/l)The amount of Na in the electrolyte (mol/l)The proportion of the residual capacity (%)
Comparative example 80,10,150
Comparative example 90,10,06 52
Example 140,10,0555
Example 150,10,0265
Example 160,10,0167
Example 170,10,00569

[0068] As can be seen from table 2, in the case of comparative examples 8 and 9, since the number of sodium ions exceeds its upper limit (i.e. 0.05 mol/l), defined by the present invention, the proportion of the residual capacity in all these cases was less than 50%. At the same time, in the cases of the examples of the present invention, although the number of aluminum ions was 0.1 mol/l, i.e. it was the same as in the comparative examples, however, because the amount of sodium did not exceed 0.05 mol/l or the upper limit defined by the present invention, the proportion of the residual capacity in all of these cases accounted for more than 50%. This may have been a manifestation of almost the same effect as if they were used selenium ions or titanium ions. In addition, although in these examples were used to fill the battery, it is also possible to achieve almost the same effect and in the case of a sealed lead batteries.

(Examples 18-54; Comparative examples 10-20)

[0069] When using Sortavala for the basics of the positive electrode, which consisted of 0.04 wt.% calcium, 1.0 wt.% tin, of 0.015 wt.% aluminum 0,008 wt.% barium, the rest lead and unavoidable impurities, were made by cast basis using the die with a vertical connector of type "book". Casting was performed with a speed of 15 pages per minute. Cast thus the foundations were subjected to heat treatment for 3 hours at a temperature of 120°C for the production of dispersion-strengthened foundations.

[0070] Then lead to the powder for positive electrode was added bismuth, calcium, tin, antimony or arsenic in different quantities to give the corresponding mixture. While bismuth, calcium and tin was added in the form of sulfate, and antimony and arsenic were added in the form of oxides. A number of these materials was set so that it matches the amount of pure metal, optionally added to the mass of the active material of positive electrodes.

[0071] Next, the paste of active material of the positive electrode prepared in the usual way using this lead powder, spread on a substrate and then exposed it to cure for 24 hours at a temperature of 40°C in an atmosphere with a humidity of 95%. After this, the resulting plate was dried, receiving plate positive electrode is not subjected to forming. Then the plates are positive electrode is, plate negative electrodes, which are not subjected to forming, which were made in the usual way, and a polyethylene separator was collected and introduced into the battery Bank. After that, prepare the electrolytes of different types when using aluminum ions, selenium ions or titanium ions in the form of sulfates. These electrolytes are appropriately introduced into the battery banks and carried out the formation of the battery cans, producing, respectively, lead-acid batteries 12 In size D23, the rated capacity of which is at a 5-hour charge was 50 And·H. In this case, the amount of added aluminum ions, selenium ions and titanium ions were changed in various ways. In the analysis of these electrolytes lead batteries that have been mentioned above formation, it was found that the concentration of sodium ions is in the range from 0.01 to 0.02 mol/L. Then these lead-acid batteries were tested for durability in conditions of idling, respectively evaluating these batteries.

[0072] First of all, these lead-acid batteries fully charged at a temperature of 25°C with rated current for 5 hours. Then these lead-acid batteries were subjected to cyclic is tested for durability in conditions of idling, which is repeated until the end of battery life, respectively, defining the number of repetitions of the loop. Namely, one cycle of this cyclic tests for service life under conditions of idling consisted of a period of the discharge direct current for 59 seconds at a current of 50 a and for one second at a current of 300 a at 25°C, and the period of charging with a constant current/constant voltage for 60 seconds at a current of 100 a and the upper limit voltage of 14.0 C. In this case, although the temperature of the battery gradually increased during the test due to dzhoulevo heat or heat of reaction, it stabilized at about 50°C. the Results are presented in tables 3, 4, 5 and 6, which also shows the results of the comparative examples.

Table 3

The battery life, in which different kinds of ions added to the electrolyte and the positive electrode (No. 1)
Additives in the electrolyte (mol/l)Additives to the cathode (wt.%)Life in idle mode
AlSeTiBiSbCaSnAs(number of cycles)
Cf is WriteLine examples 10--------15000
11---0,005----18000
12---0,01----20000
13---0,05----24000
14---0,1----24000
15---0,5----20000
16---1,0----16000
Examples180,1--- ----32000
190,1--0,005----34000
200,1--0,01----36000
210,1--0,02----38000
220,1--0,05----40000
230,1--0,1----40000
240,1--0,2----38000
250,1--0,5----33000
/p>

Table 4

The battery life, in which different kinds of ions added to the electrolyte and the positive electrode (No. 2)
Additives in the electrolyte (mol/l)Additives to the cathode (wt.%)Life in idle mode
AlSeTiBiSbCaSnAs(number of cycles)
Comparative example170,1--1,0----24000
Examples260,1--0,05--0,005-40000
270,1--0,05--0,01-41000
280,1--0,05--0,02-42000
290,1- -0,05--0,05-44000
300,1--0,5--0,1-44000
310,1--0,05--0,2-44000
320,1--0,05-1,0-44000
330,1---0,05--41000
340,1---0,050,1-45000
350,1---0,05--0,0543000
360,1----0,5--37000

Table 5

The battery life, in which different kinds of ions added to the electrolyte and the positive electrode (No. 3)
Additives in the electrolyte (mol/l)Additives to the cathode (wt.%)Life in idle mode
AlSeTiBiSbCaSnAs(number of cycles)
Comparative example180,005--0,05----29000
Examples370,01--0,05----32000
380,03--0,05----39000
390,05--0,05----40000
400,2--0,05 ----36000
410,3--0,05----31000
Comparative example190,4--0,05----24000
Examples42-is 0.0002-0,05----31000
43-0,0005-0,05----37000
44-0,001-0,05----39000
45-0,0012-0,05----39000

Table 6

The battery life, in which different kinds of ions to which aulani to their electrolyte and the positive electrode (No. 4)
Additives in the electrolyte (mol/l)Additives to the cathode (wt.%)Life in idle mode
AlSeTiBiSbCaSnAs(number of cycles)
Examples460,10,001-0,05----41000
47--0,0010,05----31000
48--0,0050,05----36000
49--0,010,05----38000
50--0,020,05----38000
51- -0,050,05----36000
52--0,10,05----32000
Comparative example20--0,20,05----22000
Examples530,1-0,010,05----42000
540,10,0010,010,05----43000

[0073] As can be seen from table 3, in the case of all examples in which the aluminum ions, selenium ions or titanium ions were not included in the electrolyte, the service life under cyclic tests were 25,000 cycles or less, even if the positive electrode was added bismuth. In the case of examples 18-25 in the electrolyte consisted of the aluminum ions in an amount of 0.1 mol/L. Among these examples, example 18 represents the case in which were not included bismuth ions, and examples 19-25 represent the keys of the cases with the inclusion of bismuth ions in different quantity. In all these examples, however, the service life in cycles was more than 25000. In particular, in the case of example 23 service life in cycles was increased to 40,000.

[0074] table 4 presents examples 26-32, 34 and 35, in which as additives to the positive electrodes were added metals of two or more species. In all these examples, the service life in cycles amounted to more than 40,000, which, respectively, testified about their significant positive effect. Also in the case of examples 33 and 36, which were added separately antimony and calcium, manifested significant positive effect. In the case of comparative example 17, in which the electrolyte contains 0.1 mol/l of aluminum ions, because the amount of bismuth, introduced as an additive in the positive electrode, was more than 1.0 wt.%, the period of service, in contrast, was getting worse.

[0075] table 5 shows that, as in the case of examples 37-41 content of aluminum ions is limited by the interval 0.01 to 0.3 mol/l, possibly increasing the service life. In the case of examples 42-45, in which the content of selenium ions was limited to the interval is 0.0002-0,0012 mol/l, it was possible increase of service life under cyclic testing to more than 30,000 cycles. Comparative examples 18 and 19 illustrate the case that if the content of aluminum ions so little as to 0.005 mol/l or as high as 0.4 mol/l, croxley during cyclic tests is reduced.

[0076] table 6 shows that if the content of titanium is limited by the interval of 0.001-0.1 mol/l, it is possible to increase the service life under cyclic testing. In addition, if the content of titanium is increased to 0.2 mol/l, as in example 20, the period of service in the idling mode is reduced. In the case of example 54, in which the electrolyte were simultaneously included the aluminum ions, selenium ions or titanium ions, it was possible increase of service life under cyclic testing up to more than 40000.

[0077] Although in these examples used a lattice basis, made by casting without application of pressure, the present invention surely can also use bases made by continuous casting or deformation processing by rolling. In addition, although each of the metals was added to the active material in these examples, in the form of sulphate or oxide, provided that the metal is soluble in an aqueous solution of sulfuric acid or in water, these metals can easily be mixed with the active material, the metals can be introduced into the active material in the form of compounds such as sulfite, carbonate, bicarbonate, phosphate, borate, hydroxide, salt metalloceramic acid. Bismuth, antimony, calcium, tin, and arsenic can be applied in the form of compounds, mentioned above, on the surface the decision is striated basis of the positive electrode with the formation of a layer of such compounds. Alternatively, these metals can be applied in the form of a coating on the surface of the lattice framework of the positive electrode. In addition, although used in these examples lead-acid batteries were made in the form of flooded batteries, it is also possible to achieve almost the same effect as described above, in the case of sealed lead batteries.

(Examples 55-60; Comparative examples 21-23)

[0078] using the same method that was described in example 3 were made of lead-acid batteries 12 In the size of D23, the rated capacity of which is at a 5-hour charge was 50 And·including the Formation of cans batteries performed at a constant content of aluminum ions in the electrolyte, comprising 0.1 mol/l, and at different content of lithium ions. In the analysis of these electrolytes lead batteries, which were made above the formation, it was found that the concentration of sodium ions is in the range from 0.01 to 0.02 mol/L. These ions of aluminum and lithium ions were added respectively in the form of sulfates. In addition, measurements were performed nominal capacity for 5 hours of charging in the case of idle mode by processing lead batteries in the same way it is for example 4.

Table 7

The battery life, which was added lithium
Kinds of metalCapacity at 5-hour charge (AR)Life in idle mode (number of cycles)
Li (mol/l)Al (mol/l)
Comparative examples21005015000
220,0205615000
Examples550,0050,15233000
560,010,15734000
570,020,16035000
580,040,16035000
590,070,15834000
600,140,15132000
Comparative example230,180,14323000

[0079] comparative PR is a measure of 22 you can see, in the case of lead batteries, which were added only lithium ions without the addition of ions of aluminum, although it had been possible to increase the nominal capacity at 5-hour charge, it was impossible to improve battery life in idle mode. At the same time, as can be seen from examples 55-60, in the case of joint adding lithium ions and aluminum ions in lead battery can be improved as the nominal capacity at 5-hour charging, and battery life in idle mode.

[0080] comparative example 23 can be seen that the addition of lithium ions in the battery in an excessive amount worsens as the nominal capacity at 5-hour charging, and the battery life in idle mode. When disassembling the lead rechargeable battery for her research, it was confirmed that the softening of the active material of the positive electrode was faster than could be expected from the number of repetitions obtained from tests on life, and that excessive introduction of lithium ions contributes to the softening of the active material.

(Examples 61-67; Comparative examples 24-29)

[0081] Lead-acid batteries were made, as described below, to confirm the effects created by adding carbon. In the spruce production of negative electrodes prior to their formation (i.e. not yet subjected to the formation) to the lead oxide, which was prepared using a ball mill, was added acetylene carbon black (type carbon black with a specific surface area of 70 m2/g and a powder of barium sulfate and formed the mixture is then subjected to dry mixing. The content of carbon powder was changed in various ways.

[0082] To the mixture was added an aqueous solution of lignin and then mixed with gradual addition of deionized water, thus forming a paste water-based. Then the paste was stirred while adding thereto a dilute sulfuric acid density of 1.36, thus forming a paste of the active material for negative electrodes. The number used in this deionized water was approximately 10 parts by weight, and the amount of diluted sulfuric acid was 10 parts by mass, calculated for both components is 100 parts by weight of lead oxide. In addition, the amount of deionized water was adjusted so that the density of the prepared pastes as measured in the cylinder was approximately 140 g/duim3. Cooked pasta, spread it on a cast base, made of an alloy on the basis of Pb-Ca, and then exposed it to cure for 24 hours at a temperature of 40°C in an atmosphere with a humidity of 95, after that dried, receiving plate, the negative electrode is not subjected to forming.

[0083] in Addition, for the manufacture of positive electrode plates, not subject formation, 100 parts by weight of lead oxide mixed with gradual addition of 10 parts by weight of deionized water and then added 10 parts by weight of dilute sulfuric acid density of 1.27, thus forming a paste of the active material for positive electrode. This paste was used so that its density when measured in the cylinder was approximately 140 g/duim3. Cooked pasta, spread it on a cast base, made of an alloy on the basis of Pb-Ca, and then exposed it to cure for 24 hours at a temperature of 40°C in an atmosphere with a humidity of 95%, and then dried, obtaining a positive electrode plate, not subjected to forming.

[0084] the Assembly of the lead battery performed as follows. Namely, comparatie separators combined with these plates not subjected to forming, and welding the plates together by a casting method on the ribbon (COS), receiving the group of plates, which were placed in the battery Bank, made of polypropylene, and closed the battery Bank by means of thermal welding. In the battery Bank has introduced ele is trolic, containing 0.1 mol/l of aluminum ions in the form of sulfate, performing, respectively, the formation of the battery, resulting in a received lead battery 12V size D23 with a capacity of 50 And·including the density of the electrolyte in this lead battery was 1,28.

[0085] Then, these lead-acid batteries fully charged at a temperature of 25°C with rated current for 5 hours. After that, these lead-acid batteries were subjected to testing at the time of service in the idling mode. The results are presented in table 8, which also shows the results of the comparative examples.

Table 8

The battery life, which has been added carbon
The amount of carbon and metalLife in idle mode (number of cycles)
Carbon

(mol/l)
Al

(mol/l)
Comparative examples240,1015000
250,2017000
260,5018000
271,0 018000
282,5018000
295,0018000
Examples610,050,128000
620,10,132000
630,20,135000
640,50,137000
651,00,138000
662,50,139000
675,00,139000

[0086] From comparative examples 24-29 shows that even if the carbon content was increased to more than 0.5 wt.%, in the case where the aluminum was not included in the battery, it was impossible to expect an increase in service life, and if the aluminum ions were included in the electrolyte, the life of idling could be greatly increased due to the synergistic action of these ions. However, increasing the carbon content of more than 0.5 wt.% an additional action was impossible. In addition, when the aluminum ions have been replaced by selenium ions and/or titanium ions, obtaining almost the same is effektov, as explained above. Although in these examples was used acetylene black, you can use carbon black of any kind, such as furnace carbon black, graphite, activated carbon and the like, provided that carbon black is conductive. The specific surface of the carbon black should preferably be not more than 300 m2/, If the specific surface area of carbon black is more to this upper limit, then during charging can cause excessive release of hydrogen, which accelerates the reduction of the electrolyte.

(Examples 68-71; Comparative examples 30-33)

[0087] Lead-acid batteries were made, as described below, to confirm the effects obtained by adding the expanding graphite. For the manufacture of plates of the negative electrode before forming the oxide of lead, which was prepared by means of a ball mill, was added acetylene carbon black with a specific surface area of 70 m2/g and a powder of barium sulfate and formed the mixture is then subjected to dry mixing. To the mixture was added an aqueous solution of lignin and then mixed with gradual addition of deionized water, thus forming a paste water-based. Then the paste was stirred while adding thereto a dilute sulfuric acid p is Amnesty 1,36, thus forming a paste of the active material for negative electrodes. The number used in this deionized water was approximately 10 parts by weight, and the amount of diluted sulfuric acid was 10 parts by mass, calculated for both components is 100 parts by weight of lead oxide. The number of deionized water was adjusted so that the density of the prepared pastes as measured in the cylinder was approximately 140 g/duim3. Cooked pasta, spread it on a cast base, made of an alloy on the basis of Pb-Ca, and then kept for 24 hours at a temperature of 40°C in an atmosphere with a humidity of 95%, and then dried, obtaining the negative plate electrodes, which are not subjected to forming.

[0088] in Addition, for the manufacture of positive electrode plates, not subject formation, 100 parts by weight of lead oxide mixed with gradual addition of 10 parts by weight of deionized water and then added 10 parts by weight of dilute sulfuric acid density of 1.27, thus forming a paste for positive electrode. The number of expanding graphite modified in various ways. This paste was used so that its density when measured in the cylinder was approximately 144 g/duim3. prigotovlennuyu paste smeared on cast basis, made of an alloy on the basis of Pb-Ca, and then exposed it to cure for 24 hours at a temperature of 40°C in an atmosphere with a humidity of 95%, and then dried, obtaining a positive electrode plate, not subjected to forming.

[0089] the Assembly of the lead battery performed as follows. Namely, comparatie separators combined with these plates not subjected to forming, and welding the plates together by a casting method on the ribbon (COS), receiving the group of plates, which were placed in the battery Bank, made of polypropylene, and closed the battery jar cover by means of thermal welding. In the battery Bank has introduced an electrolyte containing 0.1 mol/l of aluminum ions in the form of sulfate, performing, respectively, the formation of the battery, resulting in a received lead battery 12V size D23 with a capacity of 50 And·including the density of the electrolyte in this lead battery was 1,28.

[0090] Then, these lead-acid batteries fully charged at a temperature of 25°C with rated current for 5 hours, and then discharged at the rated current for 5 hours. Then these lead-acid batteries were subjected to tests for a period of service under high load in accordance with Penskymartens standard (JIS), while lead-acid batteries fully charged at a temperature of 25°C with rated current for 5 hours. After this was completed the cycle consisting of the discharge of these lead batteries at a temperature of 40°C shock 20 and the charging current of 5 amps and 5-hour rated current; the cycle was repeated until the end of battery life, while the determined number of cycles. When using these lead batteries were testing at the time of service in the idle mode; test conditions were the same as in example 3. The results are summarized in table 9.

Table 9

The battery life, which was added to the expanding graphite
Expanding graphite

(wt.%)
Metal ionsCapacity at 5-hour charge (AR)The term of service under high load (cycles)Life in idle mode (number of cycles)
Al

(mol/l)
Bi

(wt.%)
Comparative examples300005010015000
310,500555013000
32000,054818024000
330,500,055518024000
Examples680,10,10,055325040000
690,50,10,055520040000
7010,10,055718040000
7120,10,055716040000

[0091] Comparative examples 31 and 32 illustrate the cases in which respectively the expanding graphite and bismuth are used separately. When using the expanding graphite was possible increase of the efficiency of use of the positive electrodes and the increase of the nominal capacity at 5-hour charging these lead batteries. However, accelerated softening of the active material of positive electrodes and, accordingly, the military, the term of service under high load was decreased to a greater extent than in the case when was not included expanding graphite; thereby the service life of idling was reduced to less than 25,000 cycles. In the case of comparative example 33, in which the expanding graphite and bismuth are used together, although it was possible improvement in 5-hour rated capacity and service life under high load, the service life of idling was also reduced to less than 25,000 cycles. In the case of examples in which the expanding graphite and bismuth are used together for positive electrodes and the electrolyte was added to the aluminum ions, it was possible to not only increase the 5-hour rated capacity, but also improve service life at higher loads and longer service life in idle mode, suggesting a synergistic action, which can be obtained from the joint use of these materials. In addition, when the aluminum ions have been replaced by selenium ions and/or titanium ions, it was possible to obtain almost the same effects as described above. Also when bismuth was replaced by antimony or calcium, even when additionally injected tin, or when used in conjunction antimony and arsenic, it was also possible to obtain practically the same effects, as explained above. In addition, although used in these examples lead-acid batteries were made in the form of flooded batteries, it is also possible to achieve almost the same effect as described above, in the case of sealed lead batteries.

Industrial applicability

[0092] As described above, the present invention is applicable to a lead battery, which is adapted for use in a state of partial charge (SCS), when the state of charge is limited within the range from 70% to less than 100%, as, for example, in the case of idling, control, charge, hybrid systems, etc., i.e. lead to the battery, which is designed for use over a long service life.

1. Lead battery, characterized in that it contains a group of plates, placed in the battery Bank, and entered into the electrolyte, and a lead storage battery adapted for use in a state of partial charge, when the charge status is limited within the range from 70% to less than 100%; the group of plates is formed by a package consisting of a large number of bases of the negative electrode that includes a lattice basis, filled with active material, a negative the output electrodes, a large number of bases of the positive electrode that includes a lattice basis, filled with the active material of positive electrodes and a porous separator located between the negative electrodes and positive electrodes, and the electrolyte contains at least one kind of ions selected from the group consisting of aluminum ions, selenium ions and titanium ions.

2. Lead storage battery according to claim 1, in which the aluminum ions, selenium ions and titanium ions included in the electrolyte in an amount of 0.01 to 0.3 mol/l, is 0.0002-0,0012 0.001 to 0.1 mol/l, respectively.

3. Lead storage battery according to claim 1 or 2, in which the electrolyte additionally contains not more than 0.05 mol/l of sodium ions.

4. Lead storage battery according to claim 1 or 2, in which the electrolyte additionally contains from 0.005 to 0.14 mol/l of lithium ions.

5. Lead storage battery according to claim 3 in which the electrolyte additionally contains from 0.005 to 0.14 mol/l of lithium ions.

6. Lead storage battery according to claim 1 or 2, in which the foundations of a positive electrode formed from an alloy based on lead-calcium, and the base surface of the positive electrode and/or the active material of the positive electrode contains at least one kind of material selected from the group consisting of a metal selected from bismuth, antimony and calcium, and/or connect the Oia these metals.

7. Lead storage battery according to claim 3, in which the foundations of a positive electrode formed from an alloy based on lead-calcium, and the base surface of the positive electrode and/or the active material of the positive electrode contains at least one kind of material selected from the group consisting of a metal selected from bismuth, antimony and calcium, and/or compounds of these metals.

8. Lead storage battery according to claim 1 or 2, in which the active material of the negative electrode further comprises 0.05 to 5.0 wt.% of carbon.

9. Lead storage battery according to claim 3, in which the active material of the negative electrode further comprises 0.05 to 5.0 wt.% of carbon.

10. Lead storage battery according to claim 3 in which the electrolyte contains a 0.002-0.05 mol/l of sodium ions.

11. Lead storage battery according to claim 6, in which the bismuth, antimony and calcium included in the base surface of the positive electrode and/or the active material of positive electrodes in the amount of 0.005-0.5 wt.%, of 0.005 to 0.2, and 0.05-1.5 wt.% accordingly, in the calculation of the pure metal, relative to the weight of the active material of positive electrodes.

12. Lead storage battery according to claim 1 or 2, in which the active material of the positive electrode contains an expanding graphite.

13. Lead rechargeable battery is according to claim 3, in which the active material of the positive electrode contains an expanding graphite.

14. Lead storage battery according to claim 6, in which the base surface of the positive electrode and/or the active material of the positive electrode further comprises tin and/or arsenic metal and compounds in addition to the specified at least one kind of material selected from the group consisting of the metals bismuth, calcium and antimony and/or compounds of these metals.

15. Lead rechargeable battery of claim 8, in which the carbon included in the active material of the negative electrode is a carbon black, graphite or activated carbon.

16. Lead storage battery according to item 12, in which the active material of the positive electrode contains an expanding graphite in an amount of 0.1-2.0 wt.% in the calculation of the active material of positive electrodes.

17. Lead rechargeable battery 14, in which the content of tin is included in the base surface of the positive electrode and/or the active material of positive electrodes ranges from 0.005 to 1.0 wt.%, in the calculation of the pure metal, relative to the weight of the active material of positive electrodes, and the arsenic content included in the base surface of the positive electrode and/or the active material of the positive the output electrodes, ranges from 0.005 to 0.2 wt.%, in the calculation of the pure metal, relative to the weight of the active material of positive electrodes.

18. The method of manufacture of lead storage batteries, containing a group of plates, placed in the battery Bank, and entered into the electrolyte, and a lead storage battery adapted for use in a state of partial charge, when the state of charge is limited within the range from 70% to less than 100%, while the group of plates is formed by a package consisting of a large number of bases of the negative electrode that includes a lattice basis, filled with active material, a negative electrode, a large number of bases of the positive electrode that includes a lattice basis, filled with the active material of positive electrodes and a porous separator located between the negative electrodes and positive electrodes;

this method is characterized in that at least one kind of compound or metal that is soluble in an aqueous solution of sulfuric acid and contains aluminum ions, selenium ions or titanium ions injected into the active material of the positive electrode or placed in contact with the electrolyte on a plot of battery banks, thereby providing the possibility of leaching of these ions in electrolit with the formation of the electrolytic solution, which includes at least one kind of ions selected from the group consisting of aluminum ions, selenium ions, titanium ions and lithium ions.

19. A method of manufacturing a lead battery b, in which the electrolyte further comprises a 0.002-0.05 mol/l of sodium ions.

20. A method of manufacturing a lead battery p or 19, in which the foundations of a positive electrode formed from an alloy based on lead-calcium, and the base surface of the positive electrode and/or the active material of the positive electrode contains at least one kind of material selected from the group consisting of a metal selected from bismuth, antimony and calcium, and/or compounds of these metals.

21. The method of manufacturing of lead batteries in claim 20, in which the foundations of a positive electrode formed from an alloy based on lead-calcium, and the base surface of the positive electrode and/or the active material of the positive electrode further comprises tin and/or arsenic in the form of metal and/or compounds in addition to the specified at least one kind of material selected from the group consisting of a metal selected from bismuth, antimony and calcium, and/or compounds of these metals.

22. A method of manufacturing a lead battery p or 19, in which the active is the first material of the positive electrode contains an expanding graphite.

23. The method of manufacturing of lead batteries in claim 20, in which the bismuth, antimony and calcium included in the base surface of the positive electrode and/or the active material of positive electrodes in the amount of 0.005-0.5 wt.%, of 0.005 to 0.2, and 0.05-1.5 wt.% accordingly, in the calculation of the pure metal, relative to the weight of the active material of positive electrodes.



 

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Storage battery // 2276432

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2 cl

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