Method and additive for reconditioning lead battery cells

FIELD: electrical engineering.

SUBSTANCE: proposed method is used for reconditioning lead battery cells filled with sulfuric acid based electrolyte using additive based on aqueous solution of hydrogen peroxide, saccharides, and/or aldehydes, or their derivatives. Novelty is that lead battery is alternately or periodically charged and discharged in the course of electrochemical reconditioning of cells upon its treatment with some reconditioning additives based on aqueous solution of hydrogen peroxide and after main charge. Battery is charged to full possible level by current amounting to 1.1-4% of rated value and its discharge is conducted with current of 0.01-5% of rated capacity of cell or battery; as an alternative, battery is charged in two phases by current of constant magnitude. Discharge below admissible value is conducted by current amounting to 1 to 4% of rated capacity followed by charging with current amounting to 3-10% of battery capacity until voltage per cell or per any cell of battery is reduced to 1.6 V. In the process battery acquires 10-15% of its rated capacity; entire procedure is repeated two to five times. Reconditioning additive has 1 to 70 ml of sulfuric acid at density of 1 to 1.32 g·cm-3, 0.1 to 10 g of saccharides in the form of solid material and/or aldehydes, or their derivatives, 0.1 to 10 g of sodium and/or potassium bicarbonate, and/or at least one hydroxide out of group of alkali metals in the form of solid material, and 0.1 to 20 g (better 0.5 to 2 g) of disulfonic acid dinaphthyl methane disodium salt per every liter of hydrogen peroxide aqueous solution. Reconditioning additive can also incorporate 0.1 to 10 g of sodium perborate and/or tetraborate, and/or pyrophosphate in the form of solid material.

EFFECT: enhanced battery capacity exceeding primary rated value.

11 cl, 5 ex

 

The technical field

This invention relates to a method of regeneration of lead batteries with electrolyte based on sulfuric acid, during which the regenerative additive based on aqueous hydrogen peroxide solution is added to the electrolyte. Then one element or battery charged and discharged in the usual manner.

This invention also relates to regenerating additives for carrying out the method of regeneration of lead batteries, containing electrolyte based on aqueous hydrogen peroxide solution, saccharides and/or aldehydes or their derivatives. It also contains carbonates and/or hydroxides of alkaline materials or peroxyborate, tetraborate, sodium pyrophosphate.

Background of invention

Known methods of re-charging include control of voltage, current and temperature or pulse charging and discharging or the regulation of the magnitude of the current re-charging. In some way solved the problem of maintaining or even improving the battery capacity or the speed at which it is discharged. However, these methods can lead to increased deposits in the battery after the irreversible deposition of sulfates in the partial allocation of irreversible sulfates from the walls of the electrodes, which may even lead to a reduction of the lifetime of b is tarei.

Several inventions solve the problem.

Author's certificate of the Czech Republic AO No. 250340 solves the problem of attaching a static source for charging and discharging the battery. Controlled charging and discharging batteries is solved by attaching a static source, which provides protection, synchronization and interference protection, galvanic isolation and voltage switching, rectification, filtering and circuit contact switch, current sensors and the circuit of the control unit. The purpose of this connection is the ability to provide controlled charging and discharging of batteries, their separation by confirmation marks the end of charging or discharging, the opportunity to influence the characteristics of the charging by manual intervention, as well as contactless blocking functions source in case of improper connection to power supply or batteries.

In the author's testimony to the Czech Republic AO No. 219246 described circuit connections for discharge and pulse charging. The positive output of the charger the battery is connected with the input of the source of energizing pulses, the output of which is connected to the positive input of at least one rechargeable battery.

In published patent application the Czech Republic, No. PV 2001-1276 presents the means and circuit connections for charging, at meradog, United elements and collected from their batteries, and discharge is carried out in two successive phases. In the first phase, the battery is charged by a constant current, and this phase ends at the time when the voltage of the battery reaches a pre-selected upper limit. During the next phase flow the charging current is interrupted for a certain period of time during which the battery voltage decreases to the preselected lower limit due to internal discharge. Then the flow of charging current in the battery is resumed.

In published patent application the Czech Republic, No. PV 3003-95 from the Swedish applicant described a method and apparatus for charging lead acid batteries. Lead batteries are charged by repeated switching on and off devices for charging batteries. When charging batteries are acceptable intervals of about one second for the connection and disconnection. In the case of conservation of charge to charge the battery pulses, which are parts of the periods of the supply voltage at intervals of about 10 seconds. The circuit is broken through the use of automatic switch located on the primary side of the transformer.

In U.S. patent No. 6100667 sets the minimum cycle time charging system to recharge b is Tara by maximizing the time interval, during which a fully charged battery is put in a strong constant charging current. The control circuit can be monitored using AC or internal reference voltage. If you use a variable reference voltage, the duration of the charging cycle the drive circuit can be reduced even more, using the methods of compensation of the charging current.

These above-mentioned inventions describe the current state of the art, which uses different methods of charging and discharging of lead and alkaline battery or lithium ion battery. Current status of methods of charging batteries all over the world determines the types of chargers control the charging current depending on the internal resistance of the rechargeable battery (secondary source). With the gradual aging of the lead battery on its electrodes are formed irreversible sulfate, which affect the value of the internal resistance of the rechargeable battery, which leads to the error in estimating the charging current when charging. In this case, the battery charged thereby, can reach values only partial charging, which can cause damage during operation, if it is not protected from prohibited discharge.

Some additives solve the problem of increasing the capacity of the elements or with the conservation of these batteries, in particular, the lead-acid or alkaline.

For example, in the patent Slovakia No. 277838 describes an additive in powder form, which contains peroksoborat sodium, sodium pyrophosphate or epimere and is used for lead-acid batteries.

On the Czech market are well-known compounds for recycling lead acid battery filled with electrolyte based on sulfuric acid, under the trademarks AMPEL PLUS, Supervit, Mečta, etc. Due to their relatively low efficiency of these compounds had no success on the market and not left on it.

Structures on the basis of peroxide compounds produced in an aqueous solution of hydrogen peroxide, was a significant achievement in this area. Regenerating the additive of this type is described in the Czech inventions, namely copyright certificates of the Czech Republic AO 262274, JSC 271813, JSC 271814, JSC 271768, JSC 278416.

In copyright certificates of the Czech Republic No. 260591 and 272401 described method of regeneration of lead acid and alkaline batteries, which are used these regenerating supplements.

In the author's testimony to the Czech Republic AO 260591 and 272401 described method of regeneration of intact mechanical lead or alkaline battery. Regeneration is carried out by adding an aqueous solution of hydrogen peroxide certain portions of the electrolyte, although it is preferable that the item was partially charged before reg is the generation and charged in the process of regeneration.

In the author's testimony to the Czech Republic AO 272401 presents a method of regeneration of the secondary elements of lead or alkaline batteries. The electrolyte in these cells is replaced with a regenerating solution containing hydrogen peroxide in a concentration of from 0.01 to 2%. Preferably, during regeneration items was partially charged or discharged by a current with a maximum value equal to 25% of the nominal capacity of the element in ampere-hours. After regeneration regenerating solution is replaced with a new electrolyte. For alkaline batteries, it is desirable to periodically change regenerating solution and, if necessary, rinse it with distilled water.

When using these methods, regeneration is possible not only to restore the capacity of the used battery to its original state, but also to use it again the battery, which is more could not be used due to significant oxidation of the surfaces of the electrode plates.

After prolonged use of this type of regeneration and monitor the results of its application need to improve regeneration in the sense of increasing the capacity of the restored battery and extend its life.

Currently, the service life of lead acid batteries, filled with sulfuric acid, prolonged way the slow formation of the passive surface sediments on the plate electrodes of the battery. With this purpose, many different additives were added either in the electrolyte or the electrode material as a material that prevents agglomeration.

In the Czechoslovak author's certificate No. 260591 describes how regeneration is not mechanically damaged lead or alkaline battery. Regeneration is carried out by adding to the electrolyte hydrogen peroxide, the total number of added hydrogen peroxide is in the range from 0.01% to 3% of the volume of the electrolytic cell, and is used an aqueous solution of hydrogen peroxide with a concentration of from 30 to 40%.

The advantage of this technical solution is that it partially eliminates irreversible sulfate deposits, however, if you do not follow the desired ratio, the composition will be too active and can damage the separators between the electrodes and, thus, destroy the battery.

Additive for lead acid and alkaline batteries described in the copyright certificate of the Czech Republic No. 271813. The Supplement is created by combination of several compounds, of which one is taken from saccharides and their derivatives, dissolved in water, while others are peroxides.

Compared with the above-mentioned compositions of this composition represents a significant improvement and provides greater efficiency and deceleration process is sa, that is especially important for starter batteries.

The disadvantage is that it does not solve the problem of removal of the hardened layers of irreversible sulfate from the surface of the electrodes of the battery.

In the Czech patent No. 278416 describes an additive for lead batteries with electrolyte based on sulfuric acid. This Supplement contains peroksoborat sodium in an amount of from 50 to 70% by weight, piratefest sodium in an amount of from 15 to 48% by weight, disodium salt ginatilan dissolvability in an amount of from 1 to 15% by weight and glycide or epimer in an amount of from 1 to 20% by mass.

This regenerating additive was tested, but was not successful. The above disodium salt ginatilan dissolvability cannot be stored in an aqueous solution containing peroxide and other compounds, without the stabilizing solution. Therefore, this salt was used only in powder form. Its disadvantage is the instability during storage, as the disodium salt ginatilan dissolvability mixed with peroksoborat sodium and hydrogen peroxide can react by themselves, even at temperatures above 30°that leads to the decomposition of regenerating supplements. They also very quickly become unwanted reaction inside the lead element, and this may damage the separators between the electrodes of the battery.

Insufficient is OK regenerating supplements proposed patent of the Czech Republic No. 278416, is that the composition with the formula reacts slowly and for a long time, and this only seeps on the surface of the material of the electrodes, particularly in the batteries, the electrodes are protected textile materials.

In the Czech patent No. 292524 that share of the patent that describes the recycling additive for lead acid batteries, which contains from 1 to 70 ml of sulfuric acid with a density of from 1.01 to 1.35 g·cm-3from 0.1 to 10 g of sugars and/or aldehydes or their derivatives in the form of solids from 0.1 to 10 g of sodium bicarbonate and/or potassium and/or at least one hydroxide from the group of hydroxides of alkali metals in the form of solids per liter of aqueous hydrogen peroxide solution with a concentration of from 1 to 40%. In addition, the additive contains from 0.1 to 10 g peroxoborate sodium, and/or tetraborate sodium and/or sodium pyrophosphate. This regenerating additive significantly outperforms previous technical solution. Its advantage lies in the uniform regeneration of the electrodes of the battery.

However, in the two-year observation of the use of this regenerating supplements suggested in the patent, the Czech Republic, No. 292524, it was found that in some cases, for example, with a very hard surface plate the electrodes, its effectiveness is negligible.

In CS AO No. 186387 describes the use of a mixture that contains at least 90% dinaftiletilena and from 0.1 to 9.9% of sulfuric acid and sodium sulfate in a mixture with an arbitrary ratio, with the maximum number of process impurities 5%. This mixture is added to the active mass and/or the electrolyte of the new lead battery. According to this invention, this mixture has a dispersing effect is 2-3 times higher than similar indicator beech powder or Kortan QD, allows for a more rapid discharge at low temperature and to increase the service life of the starter battery during the classical cycle. This invention relates only to the manufacture of new batteries, namely starter batteries, operating at low temperatures, and processing of the electrolyte in the new battery.

This mixture does not contain hydrogen peroxide and other oxidizing or reducing additives, such as sugars and/or aldehydes, carbonates and/or hydroxides of alkali metals or peroksoborat, tetraborate or sodium pyrophosphate. This mixture is not suitable for regeneration of used batteries or elements and to increase their capacity.

Summary of the invention

The purpose of this invention is a method for the regeneration of lead acid batteries the electrolyte based on sulfuric acid, when the electrolyte is added regenerating additive based on aqueous hydrogen peroxide solution, and then at least one element or battery charged and discharged in the usual way. The essence of this invention lies in the fact that at least one element or the battery is being charged above the level of a full charge through the cyclic charging and discharging, lasting only from 10 to 70 hours, with at least one element or battery charged for 15-20 minutes current components from 1.1 to 4% of the rated capacity of the element or the battery and discharge it for 0.5-2 minutes shock, comprising from 0.01 to 5% of the nominal capacity of the element or rechargeable battery.

The main advantage of this method is to increase the capacity of the battery is significantly above its initial nominal value and that the chemical treatment of the surface layer of the electrodes using a peroxide-based solution of hydrogen peroxide you can use different methods, greatly reducing the charge is above the limit of the main charge or lower limit of the discharge and raising it above the level reached during its creation. The method of electrochemical regeneration of lead acid batte is Torno batteries filled with an electrolyte based on sulfuric acid, in combination with the proposed in this invention means charging, significantly increase the regeneration effect and create the opportunity for multiple recovery. Thanks to life extension elements or rechargeable batteries reduces the amount of hazardous waste that contributes to the improvement of the ecological situation.

The regeneration according to the invention leads to a complete change in the electrode surface, to soften their surface, which leads to the increase of active functional area of the electrodes, the magnitude of which depends on the capacity of the element or the battery. For example, if the passport of the new battery, issued by the manufacturer, specified capacity of 120 A·h, it is possible to increase the nominal value of up to 150 And·h after using the regeneration method in accordance with this invention, and its service life can be increased in two times. The advantage of this method of regeneration proposed in this invention, consists in the possibility of its recurrence.

Cyclic charging and discharging within a certain time interval defined by the current changes as the electrolyte so that the conductive particles are converted into a non-conductive particles, which reduces the self-discharge element or b is tarei. The current values of the charging and discharging are or are selected sparing with the intention that the electrodes are not damaged by, for example, bending or other deformation; because, if the plate electrodes of the battery are hard, they are damaged with significant current and long-term impact.

Lower limit charging current is selected so that the item did not occur electrochemical changes. Upper limit of the charging current is chosen so that the element or the battery is not overheated during charging. When using regenerative additives and cyclic recharge element or the battery pack "irreversible" surface sulfate deposits effectively decompose and dissolve.

Discharge current that passes charging current, you can use because it operates within much less time, allowing you to lower the voltage between the electrolyte and electrode elements. In General, a zero value of the discharge current means the interruption of charging, during which the battery voltage returns at or near voltage open circuit.

Periods of time during which the function of charge and discharge currents, determined based on the optimal estimation and experimental tests./p>

Obtaining at least one item or a rechargeable battery, charged above the level of full charge is achieved by the cyclic charging and discharging, lasting only from 10 to 70 hours, with at least one element or battery cyclically charged for 15-20 minutes and are discharged within 0.5 to 2 minutes, and the process occurs in two phases, during the first phase, the charge current, comprising 1,1-4%, and the discharge current of 0.01-5% of the rated capacity of the element or rechargeable battery and during the second phase, the current decreases during charging to 1.1-3%, and during discharge to 0-4% of the nominal capacity of the element or rechargeable battery.

The advantage of this method of regeneration is carried out in two phases, which is proposed in this invention, consists in the additional capacity of the element or the battery. The implementation of the charging member or a battery in two phases allows to use large charge and discharge currents in the first phase and smaller currents in the second phase, which is beneficial to the battery. For example, in the second phase, with smaller current, you can achieve a softer structure of the electrode surface.

The advantage is that when at least one element or AK is amulatory the battery is further charged with a constant current, components 1.1 to 2.1% of the nominal value of capacitance element or the battery for 20 to 50 hours.

Advantage is also that between the first and second phases of charging at least one element or the battery is partially discharged by a current, comprising 10-30% of the nominal battery capacity within 2-10 minutes. It is possible to charge with a constant current having the above-mentioned low values lying in the range of 1.1-2.1 per cent without damaging the surface of the battery, but the decomposition and dissolution of unwanted lead sulfate on the surface of the electrodes. In addition, while the described process results in the release of atomic hydrogen, which clears the lead electrodes.

The advantage is that at least one element or the battery is partially discharged by a current, comprising from 10 to 30% of the nominal battery capacity, within 2-10 minutes before charging with a constant current. This discharge is carried out in the specified mode, creates feedback in the battery and contribute to the erosion of the surface due to the formation of solid sulfates.

The advantage is the fact that before restoring at least one element or battery charging current of 5-10% of the value E. the bones of the battery, up until the item or the battery will not be fully charged, i.e. to a value of 2.45 In each item for acid elements. Such charging is used in the case of the hardened plate electrodes in a stationary batteries with electrodes of large area. In this case, when charging a large current without the use of such modifications they can easily be deformed. In practice, the backup batteries were observed frequent bending and other deformation of the hardened electrode element. Such changes occur when the battery is flat after a break in the power supply with the subsequent charging using the standard charger, which is normally set to the value specified by the manufacturer. Electrodes, hardened normally, therefore, are no longer functional and cannot withstand normal current load without interruption.

Alternative technical solution represents the regeneration of the lead-acid battery, discharged to below the allowable discharge level (1.8 V lead items), during which the regenerative additive based on aqueous hydrogen peroxide solution is added to the electrolyte. The essence of this alternative way of regeneration, according to this invention, is that the element or all but cumulativa battery, consisting of elements is discharged below the allowable level of discharge, is restored by the cyclic charging and discharging, during which it is discharged within 2-10 minutes shock comprising 1-4% of the battery capacity, and subsequently charged within 1-2 minutes of shock, comprising 3-10% of the battery capacity, and this is to reduce the voltage to 1.6 In the element or each element of the battery. When the battery gets 10-15% of the nominal capacity. This whole procedure is repeated two to five times.

The alternative discharging and charging suitable for items where the lower limit of the discharge is reduced to 1.6 In one item for acid elements. As a result, he gives the same effect as charging the battery above the limit of complete recharge element. This alternative way of regeneration, according to this invention, requires more attention and monitoring of measured values.

The regeneration process proposed in this invention can be repeated in accordance with necessary for the operation of the battery.

The regeneration method proposed in this invention, is not suitable for regular recharging of the battery, although it is advantageous to use, if necessary, align the capacities of battery cells.

Charging method of the restored battery, coz the ACLs this invention, it is advantageous to carry out using compounds peroxides formed by using an aqueous solution of hydrogen peroxide and described, for example, in AO 260591, JSC 263221, JSC 262274, JSC 271768, JSC 271814 and JSC 272401, so the battery after the implementation of regeneration and after the main process of charging and discharging, preferably current, comprising at least 8% of the nominal value of the battery to indicate a fully charged cell or battery to a voltage of 2.45 In one item for acid battery or lithium ion battery.

The above disadvantages of the known regenerative additives completely eliminated or significantly reduced when using regenerative additive for lead acid batteries with electrolyte based on an aqueous sulfuric acid solution proposed in this invention, the essence of which is that regenerating additive contains from 1 to 70 ml of sulfuric acid with a density of from 1 up to 1.32 g·cm-3, 0.1-10 g of sugars in the form of solid substances and/or aldehydes or their derivatives, from 0.1 to 10 g of sodium bicarbonate and/or potassium and/or at least one hydroxide from the group of hydroxides of alkali metals in the form of solids, and it can also contain 0.1 to 10 g peroxoborate sodium and/or sodium tetraborate, and/or pyrophosphate of sodium, and contains 0.1 to 20 g dvunatrievogo salt ginatilan dissolvability in the IDA solids per liter of an aqueous solution of hydrogen peroxide concentration of from 1 to 40%.

In a preferred embodiment, regenerating additive contains from 0.5 to 2 g disodium salt ginatilan dissolvability in the form of solids. Regenerating the additive may contain 0.1 to 5 g 10-50% aqueous solution of hydroxy-lignin and/or liquid sulfite.

The main advantage of the new regenerating additives proposed in the present invention is to increase the battery capacity to a value that far exceeds its original rated capacity, by using a new method of regeneration of a battery in accordance with the proposed invention. The regenerating action of the additive increases the controlled repetition of charging and discharging, in accordance with this invention. This new recycling additive accelerates the regeneration process. Significant improvement of regeneration in General and in particular in the case of lead batteries, severely damaged due to the formation of solid sulfates on the surface of the electrodes is achieved by using regenerative supplements containing compound disodium salt ginatilan dissolvability in the acid solution; and it is chemically stable, and no other component does not react in the presence of hydrogen peroxide.

Disodium salt ginatilan dissolvability is always added to the key is to scrap the solution of hydrogen peroxide with sulfuric acid in the form of solids. If you adhere to these terms and conditions, disodium salt ginatilan disulfonate can be added in any order with other components. The most suitable is the addition of this product as the last component. It can be added in a mixture with solid products other additives.

The specified number of disodium salt ginatilan dissolvability, even in the minimum allowable concentration, helps to dissolve the flakes and salt deposits on the plate electrodes of the battery. This highly effective product suitable for stationary batteries. Natural polymeric products derived from hydroxy-lignin or liquid sulfate obtained, for example, as waste during processing of wood, are slower compared to the disodium salt ginatilan dissolvability, although they are more suitable for the regeneration of starter batteries with weak electrodes smaller thickness.

The hydrogen peroxide reacts with irreversible sulphides of lead, sugars and/or aldehydes or their derivatives can be added either directly in the form of a solid technically pure chemical compounds, or, if it is more convenient, in the form of a solution. Sugars and/or aldehydes enhance the effects of regeneration. Sodium bicarbonate and/or potassium and/or hydroxide from the group of alkali metals, a sodium hydroxide, potassium hydroxide and lithium hydroxide, are effective ingredient in regenerating additive that significantly improves the quality of the regeneration process. These components can also be added in the form of a solid technically pure chemical compounds or, if it is more convenient, as their respective solutions. Adding sulfuric acid plays a stabilizing role in regenerating solution, without which the reaction in solution would have started before it will add to the battery.

Peroksoborat, tetraborate and sodium pyrophosphate increase the effect of regeneration, and slows down and regulate flowing in the battery is a chemical reaction that prevents damage to the separators.

Peroksoborat, tetraborate and sodium pyrophosphate can also be added in the form of a solid technically pure materials or, if more convenient, their respective solutions.

Regenerating additive designed in such a way that it was easy to add elements of the battery, and it consists of a single liquid component comprising an aqueous solution of hydrogen peroxide and sulfuric acid, which is dissolved or interact with each other sugars and/or aldehydes or their derivatives, sodium bicarbonate and/or potassium and/or lithium hydroxide, and peroksoborat, tetraborate, and sodium pyrophosphate.

Recycling is obaka is added to the electrolyte of the battery or in the form of a concentrate, either in the form of a solution, in accordance with the purpose of regeneration. For example, during operation of the battery is more convenient to add dissolved regenerating Supplement, perhaps even many times, and, of course, within the boundaries of the low concentrations, corresponding to the amount of the claims of this invention. Concentrated solutions are added for faster implementation of regeneration, after which it is possible to obtain a restored battery.

Regenerating additive designed for safe storage and considerable durability and consists of two components, which is an aqueous solution of hydrogen peroxide and sulfuric acid and a solid component consisting of saccharides and/or aldehydes or derivatives thereof, sodium bicarbonate and/or potassium and/or lithium hydroxide, and peroksoborat, tetraborate, and sodium pyrophosphate.

Examples of embodiment of the invention.

Example 1

Traction battery OPzS 160 with a nominal voltage of 48 V and a nominal capacity (Cn) 240 And·h was used for 6 years in a non-standard mode and found an overall reduction in capacity to approximately 20% of nominal.

This battery was restored by regenerating supplements suggested in the patent, the Czech Republic, No. 292524, so that regenerating additive was added in two stages: first, 30 ml, and then 40 ml was added in the first is olavina elements after modification of the electrolyte with an interval of 15 minutes.

After the decay of a chemical reaction after about 20 minutes of the first half of the elements of the battery charging current 30 And before the flue gas, and then charged the charging current of 5 amps for 60 hours in the usual way. Achieved 92% of its nominal capacity.

This regenerating additive it was made one liter of 35% hydrogen peroxide solution to which was added 70 ml of sulfuric acid with a density of 1.28 g·cm-3and then 1 ml of 30% aqueous formaldehyde and 2 g of technically pure sodium hydroxide and/or potassium hydroxide. Regenerating the solution was mixed and after stirring was ready for use.

The second half of the elements of the battery was restored by regenerating additives having the same composition as in the previous example, with the difference that regenerating additive additionally contained 2 g disodium salt ginatilan dissolvability to 1 liter. The regeneration process was the same as in the first half of the elements of the battery, but when this was achieved the capacity component 112% from the nominal value.

This second half of battery cells were recovered, in addition, in accordance with the proposed invention, as follows.

The second half of the elements of the battery was repeatedly charged the ü in accordance with the invention therefore, first they were charged to the level of full charge current 11 And for 15 hours. Then they alternately charging and discharging, according to this invention, so that after 20 minutes of charging current of 5 amps (3,125% of the nominal battery capacity) they always were discharged within 1 minute current of 6 A (3,75% of the nominal battery capacity), and the whole process of charging and discharging was repeated for 20 hours. Then the battery was further charged so that after 20 minutes of charging current of 3 A (1,87% of the nominal battery capacity) she always was discharged within two minutes the current 4 A (2.5% of the nominal battery capacity), and the whole process lasted for an additional 24 hours.

The result was a larger capacity battery, up 132% from the value of its rated capacity.

Example 2

Composition for lead batteries prigotovleniya so that the first 60 ml of sulfuric acid density of 1.24 g·cm-3was added to one liter of 30% aqueous hydrogen peroxide solution. Then to the resulting solution were added 10 g of sugars in the form of technically pure glucose and 1 g of technically pure sodium bicarbonate and 2 g disodium salt ginatilan dissolvability. The mixture was mixed until then, until it dissolved all the ingredients, and at this time regenerating additive was ready for use.

Traction ACC the battery the battery with a nominal voltage of 24 V and a nominal capacity of 400 And· h, which was used for five years, and its capacity has decreased below 30% from the nominal value, was restored by regenerating the additives according to this invention. The composition was added to each of the elements in two stages with 10-minute intervals after the establishment of the levels of the electrolyte in the battery cells. At each stage was added 80 ml of regenerating supplements. After stopping the chemical reaction in approximately 20 minutes, the battery was charged by a current of 50 a to start the selection gases. Then the battery was restored by reloading its current 8 a for 60 hours. The result of regeneration was the alignment of the containers of the elements of the battery capacity after regeneration was achieved 102% of the nominal value.

After measuring the capacity of this battery was subjected to further regeneration, in accordance with the invention, by charging and discharging at the level of the standard discharge so that the discharge was carried out by a current of 5 amps (1.25% from the nominal battery capacity) and after 10 minutes she was charged and within 2 minutes the current 16 a (4.0% of the nominal battery capacity) to reduce the voltage to 1.6 V in the weakest element. This process could continue for approximately 30 minutes. Then the battery got a charge of 10% of its capacity, and the process of discharge and the dawn of the CI was repeated three times. Then the battery was discharged current of 16 a to the level of full charging and discharging current of 48 A (12% of the nominal battery capacity) for 10 minutes and repeatedly charged by a constant current of 3 a for 18 hours.

When measuring capacitance, it was found that the capacity was increased by 118%.

Example 3

Battery OPzS battery with a nominal voltage of 12 V and a nominal capacity of 280 And·h began to operated 8 years ago, he served for 12 months, and then was stored without electrolyte, which was out of her cast. Due to long-term storage plate electrodes were damaged by deposits of irreversible sulfates.

4 years later, this battery was restored by regenerating following additives composed of 10 g of technically pure sodium bicarbonate, 70 ml of sulfuric acid having a density of 1.28 g·cm-35 g of sugars in the form of solid glucose and 5 g of technically pure sodium tetraborate added to 1 l of 30% aqueous hydrogen peroxide solution. Sodium tetraborate can fully or partially replace the diphosphate or peroksoborat sodium. And, finally, was added 3 g of disodium salt ginatilan dissolvability.

This battery was stored for 8 years in non-standard conditions, and the electrodes were heavily oxidized. After repeated additions of portions p is generating additives and after charging the standard way was reached capacity, component 102% of nominal.

This battery was restored in accordance with the invention in two phases. In the first phase it was charged by a constant current of 4.5 a (1.6% of the nominal battery capacity). For recharge were used charger Czech company Condata, with a special regime recharge negative pulse for 20 hours, and this ended the first phase of regeneration in accordance with the invention. Before recharging the second phase the battery is discharged by a current of 50 A (17,85% of the nominal battery capacity). The second phase of recharging the battery is alternately charged and discharged in accordance with this invention so that after 20 minutes of charging current of 8 A (2,85% of the nominal battery capacity) it is always discharged in one minute by a current of 12 A (4.28% relative to the nominal battery capacity), and this complete cycle of charging and discharging was continued for 24 hours. After charging was performed for measuring capacitance, which showed that the battery capacity was at the level of 120% of the rated value.

Example 4

In the previous examples described regenerating additive was one-and had the appearance of an aqueous solution of hydrogen peroxide and sulfuric acid, in which were dissolved or reacts to each the e components.

In this example, the proposed recycling additive is binary, one component is a liquid and the other solid.

The liquid component consists of an aqueous solution of hydrogen peroxide and sulfuric acid in which from 93 to 99% hydrogen peroxide with a concentration of from 1 to 40%, and from 1 to 7% sulfuric acid with a density of from 1 up to 1.32 g·cm-3.

A solid component contains from 20 to 60% of solid sugars and/or aldehydes or their derivatives, from 15 to 50% by weight of solid sodium bicarbonate and/or potassium carbonate or lithium carbonate, and from 20 to 60% by weight of the solid peroxoborate sodium and/or sodium tetraborate, and/or diphosphate sodium. The first component also contains 0.3 to 10 g 10-50% aqueous solution of hydroxy derivatives of lignin and/or liquid sulfite.

First the battery is added to the solid component. For every liter of battery electrolyte is added from 0.3 to 15 g of this component. Then, for every liter of battery electrolyte is added from 30 to 70 ml of the liquid component in the form of two successive portions, i.e. regenerating additive is created directly in the electrolyte.

A chemical reaction in the battery occurs within 15-20 minutes, then the battery starts charging current, comprising, for example, 0.1% of nominal capacity. When after charging the battery begins from the gas taken, the final charging the battery is a standard way of charging current, comprising 1-2% of the value of its rated capacity.

This type of recycling additive suitable for all types of lead batteries with electrolyte based on sulfuric acid.

In this example, the described regenerative additive was used in the standard J2 battery with a capacity of 72 And·h and 24 volts, the capacity of which has decreased and amounted to 35% of the nominal value, so that 12 g of solid regenerating component in the form of a powder prepared by mixing 30 g of commercially pure glucose, 15 g of sodium bicarbonate and 55 g of peroxoborate sodium, was added to each element of the battery. After about 10 minutes after that, each element was added 15 ml of 35% aqueous hydrogen peroxide solution stabilized with sulfuric acid, i.e. containing 5 ml of sulfuric acid density of 1.28 g·cm-3for each liter of 35% aqueous hydrogen peroxide solution. Then the battery was repeatedly charged and discharged and, in the end, was charged charging current. During the capacitance measurement of the battery capacity amounted to 106% of its nominal value.

Then this battery was subjected to further recovery in accordance with the invention as follows. Rechargeable battery charger, side buttons the up current 5,7 And 8% of the nominal battery capacity) before intense emission of gases from the electrodes. Then the battery immediately discharged current 10,8 (15% of the nominal battery capacity) for 7 minutes. After that, the battery is charged in two phases DC 1.3 a (1.8% of the nominal battery capacity) for 20 hours. Then the battery was disconnected for 10 minutes.

In the next phase the battery is charged by a constant current of 1.5 A (1.5% of the nominal capacity of the battery) for an additional 40 hours.

Final full battery capacity amounted to 114% of the nominal capacity.

Example 5

Used regenerating additive in accordance with the invention, as described in Example 1, but with the difference that the aqueous hydrogen peroxide solution has a concentration of from 1 to 10%. This regenerating additive suitable for gradual regeneration during operation of the battery. Instead of the usual topping of evaporated electrolyte distilled water this regenerating additive as needed is added to the battery.

In this example, the recycling additive for lead acid batteries were prepared as follows: 60 ml of sulfuric acid with a density of 1.28 g·cm-3was added to 1 liter of 10% aqueous solution of hydrogen peroxide. To the resulting solution were added 5 g of sugars in the form of technically pure glucose and 1 g of commercially pure bi is carbonate sodium. The last was added 2 g of disodium salt ginatilan dissolvability.

The mixture was mixed, and regenerating additive was ready to use.

This regenerating additive was used in the lead battery, and it is in the starter battery with a capacity of 55 a·h and a voltage of 12 V, which upon expiration of the warranty period for the entire lifetime instead of distilled water regularly which was then filled with regenerating additive. Consider the battery has been used for more than 5 years after the warranty period, and had a good starting characteristics even at temperatures below -20°C.

In this example the regenerating additive that was used in the starter battery during its operation. If there was a need to increase the capacity of such batteries, you would have to disable it and display of operating status for recovery procedures according to the method proposed in this invention. In this case, the closest option regeneration would be the Example 1, however, the levels of the currents should be about 1/3 from the one described, and the periods of charging and discharging should remain the same.

The above examples are not exhaustive, and there may be other combinations within the scope and essence on the frame of the technical solution, which sought to protect.

Industrial applicability

The way the regeneration of lead acid batteries with electrolyte based on sulfuric acid is suitable for use in industry, stationary, lighting, traction and starter batteries, and for home use with the purpose of extending the life of the components or all of the batteries.

The proposed recycling additive suitable for all types of lead batteries, filled with sulfuric acid.

1. The way the regeneration of lead acid batteries with sulfuric acid electrolyte in which the electrolyte is added regenerating additive based on aqueous hydrogen peroxide solution, then at least one item or the battery is being charged and discharged in the usual manner, characterized in that by means of cyclic charge and discharge cycles lasting a total of from 10 to 70 hours, creates at least one element or the battery charge is above the level of a full charge, while charging occurs within 15-20 min current, comprising 1,1-4% of the rated capacity of the element or the battery, and the discharge for 0.5-2 min current components of 0-5% of the nominal capacity of the element or rechargeable battery.

2. The way the reg is the generation according to claim 1, characterized in that at least one element or battery then charging current of constant value, comprising from 1.1 to 2.1% of the nominal capacity of the element or battery within the next 20-50 hours

3. The regeneration method according to claim 1, characterized in that by means of cyclic charge and discharge cycles lasting a total of from 10 to 70 hours, creates at least one element or the battery charge is greater than the full charge, and cyclic charging, lasting from 15 to 20 min, and discharge, lasting 0.5 to 2 min, carried out in two phases and the first phase, the charge current, comprising 1,1-4%, and the discharge is carried out by the current components of 0-5% of the nominal capacity of the element or rechargeable batteries and the second phase current is reduced during charging to 1.1-3%, and during charging to 0-4% of the nominal capacity of the element or rechargeable battery.

4. The regeneration method according to claim 3, characterized in that at least one element or battery then charging current of constant value, comprising from 1.1 to 2.1% of the nominal capacity of the element or battery within the next 20-50 hours

5. The regeneration method according to claim 3, characterized in that between the first and second phases regen is then, at least one element or battery partially discharged current, comprising 10-30% of the nominal battery capacity, within 2-10 minutes

6. The regeneration method according to claim 4, characterized in that before charging with a constant current, at least one element or battery partially discharged current, comprising 10-30% of the nominal battery capacity, within 2-10 minutes

7. The regeneration method according to one of the preceding claims 1 to 6, characterized in that at least one element or the battery before restoring the charging current of 5-10% of the battery capacity, up until the item or the battery will not be fully charged, that is, until the voltage values of 2.45 In one item for acid battery or lithium ion battery.

8. The way the regeneration of lead acid batteries, during which adds regenerating additive based on aqueous hydrogen peroxide, after which at least one element or the battery is being charged and discharged in the usual manner, characterized in that the element or all consisting of such elements rechargeable battery with charge below an acceptable level of discharge, is restored by the cyclic charging and discharging during which they are discharged within 2-10 min shock, stood at the gates 1-4% of the battery capacity, and after that charged within 1-2 min current, comprising 3-10% of the battery capacity, and this process continues to reduce the voltage to 1.6 V per element or any element of the battery, and the battery gets 10-15% of the nominal capacity, and the whole procedure is repeated two to five times.

9. Regenerating additive for implementing the method of regeneration of lead batteries with sulfuric acid electrolyte, during regeneration of the electrolyte is added regenerating additive based on aqueous hydrogen peroxide, prepared from a mixture containing an electrolyte consisting of an aqueous solution of sulfuric acid and hydrogen peroxide, saccharides and/or aldehydes or their derivatives, as well as carbonates and/or hydroxides of alkali metals or peroxoborate, tetraborate and sodium pyrophosphate, then at least one item or the battery is being charged and discharged in the usual manner according to any one of claims 1 to 8, characterized in that it contains to 1 liter of an aqueous solution of hydrogen peroxide with a concentration of from 1 to 40%: from 1 to 70 ml of sulfuric acid with a density of from 1 up to 1.32 g·cm-3from 0.1 to 10 g of sugars in the form of solids, and/or aldehydes or their derivatives, from 0.1 to 10 g of sodium bicarbonate and/or potassium and/or at least one hydroxide from the group of hydroxides of alkali metal is in the form of solids, and from 0.1 to 20 g disodium salt ginatilan dissolvability, and it may also contain from 0.1 to 10 g peroxoborate sodium and/or sodium tetraborate, and/or pyrophosphate of sodium in the form of a solid substance.

10. Regenerating additive according to claim 9, characterized in that it contains from 0.5 to 2 g disodium salt ginatilan dissolvability.

11. Regenerating additive according to claim 9 or 10, characterized in that it contains from 0.1 to 5 g aqueous solution of hydroxy derivatives of lignin and/or liquid sulfite.

Priorities:

30.04.2003 - claims 1 to 8;

10.03.2003 - PP-11.



 

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