US20060145664A1 - Method of regenerating lead battery cells and regenerative agent for performing of this method - Google Patents

Method of regenerating lead battery cells and regenerative agent for performing of this method Download PDF

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Publication number
US20060145664A1
US20060145664A1 US10/548,468 US54846804A US2006145664A1 US 20060145664 A1 US20060145664 A1 US 20060145664A1 US 54846804 A US54846804 A US 54846804A US 2006145664 A1 US2006145664 A1 US 2006145664A1
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battery
cell
current
capacity
charged
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Jan Mrazek
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AKUROS SRO
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Akuros sro
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Priority claimed from CZ2003699A external-priority patent/CZ2003699A3/cs
Priority claimed from CZ20031205A external-priority patent/CZ20031205A3/cs
Application filed by Akuros sro filed Critical Akuros sro
Assigned to AKUROS S.R.O. reassignment AKUROS S.R.O. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MRAZEK, JAN
Publication of US20060145664A1 publication Critical patent/US20060145664A1/en
Priority to US12/318,088 priority Critical patent/US7750603B2/en
Abandoned legal-status Critical Current

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/06Lead-acid accumulators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/24Alkaline accumulators
    • H01M10/30Nickel accumulators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/42Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/42Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44Methods for charging or discharging
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/54Reclaiming serviceable parts of waste accumulators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00Electrolytes
    • H01M2300/0002Aqueous electrolytes
    • H01M2300/0005Acid electrolytes
    • H01M2300/0011Sulfuric acid-based
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00Electrolytes
    • H01M2300/0002Aqueous electrolytes
    • H01M2300/0014Alkaline electrolytes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/84Recycling of batteries or fuel cells

Definitions

  • the invention concerns the method of regenerating lead battery cells with sulfuric acid electrolytes and alkaline battery cells filled with potassium hydroxide during which the regenerative agent on the basis of aqueous hydrogen peroxide is added to the electrolyte. Then at least one cell or storage battery is charged and discharged in the regular manner.
  • the invention concerns the regenerative agent for lead batteries, containing an electrolyte of an aqueous solution of hydrogen peroxide, saccharides and/or aldehydes or their derivatives. It also contains bicarbonates and/or hydroxides of alkaline metals or peroxoborate, tetraborate, sodium pyrophosphate.
  • Familiar recharging methods include watching the voltage, current and temperature or impulse recharging and discharging methods or the regulation of the size of the recharging current.
  • Familiar recharging methods include watching the voltage, current and temperature or impulse recharging and discharging methods or the regulation of the size of the recharging current.
  • the Czech Author's Certificate AO no. 250 340 solves the connection of a static source for the charging and discharging of a battery.
  • the controlled charging and discharging of the battery is resolved by connecting a static source that contains protection, synchronization and anti-jamming, galvanic separation and voltage transfer, rectification, filtration, and contact reversal circuits, current sensors and a control unit circuit.
  • the purpose of this connection is the possibility of the controlled charging and discharging of batteries, its disconnection by assessment of the end marks of charging or discharging, the possibility of influencing the charging characteristics with manual intervention and the contactless blocking of the source functions when incorrectly connected to the power supply or battery.
  • the Czech Author's Certificate AO no. 219 246 describes the connection for the recharging and pulse charging of batteries.
  • the positive output terminal of the storage battery charger is connected to the inlet of the source of recharging impulses, whose outlet is connected to the positive input terminal of at least one storage battery.
  • the publicated Czech patent application no. PV 2001-1276 presents a method and connection for charging at least two connected cells and the batteries assembled from them with the charging proceeding in two consecutive phases.
  • the battery In the first phase the battery is charged by a constant current and this phase is ended at the moment the voltage of the batteries reaches a previously-chosen upper limit.
  • the flow of the charging current is interrupted for a period during which the voltage of the battery is decreased to a previously-chosen lower limit by internal discharging. Then the flow of the charging current of the battery is restored.
  • U.S. Pat. No. 6,100,667 establishes the minimization of the time of the charging cycle of the battery recharging system by maximizing the length of time for which this high constant charging current is applied to a dead battery.
  • the control circuit can be controlled by a constant or variable internal reference voltage. If a variable internal reference voltage is used, the time of the charging cycle of the control circuit is further minimized by the compensatory technology of the charging current.
  • AO 260 591 describes the method of regeneration of mechanically undamaged lead and alkaline battery cells.
  • the regeneration is carried out by adding an aqueous solution of hydrogen peroxide in batches to the aqueous solution of the electrolyte, though it is suitable for the cell to be partially charged before regeneration and recharged in the process of regeneration.
  • AO 272401 presents a method of regenerating secondary cells of lead and alkaline storage batteries.
  • the electrolyte in the cells is replaced by a regeneration solution containing hydrogen peroxide in a concentration of from 0.01% to 2%.
  • a regeneration solution containing hydrogen peroxide in a concentration of from 0.01% to 2%.
  • the regeneration it is suitable for the cells to be partially charged or discharged with a current with a maximum value of 25% of the nominal value of the capacity of the cell in ampere-hours.
  • the regeneration solution is replaced by a new electrolyte.
  • For alkaline cells it is advisable to repeatedly change the regeneration solution while rinsing it with distilled water if necessary.
  • the additive for lead and alkaline batteries is described in the Czech Author's Certificate no. 271 813.
  • the additive is created by a combination of compounds from which one is saccharides and their derivatives dissolved in water and the others are peroxide compounds.
  • this preparation represents a considerable improvement, increased effectiveness and a slowdown in the process which is particularly advantageous for starting batteries.
  • a disadvantage is that it does not solve the removal of the hardened layers of irreversible sulfatation from the surface of the battery's electrodes.
  • the additive contains sodium peroxoborate in the amount of 50% to 70% of the mass, sodium pyro diphosphate in the amount of 15% to 48% of the mass, bisodium dinaphtylmethane disulfonic acid salt in the amount of 1% to 15% of the mass and glycides or their epimers in the amount of 1% to 20% of the mass.
  • a regenerative agent for lead batteries contains 1 ml to 70 ml of sulfuric acid with a density of 1.01 to 1.35 g ⁇ cm ⁇ 3 , 0.1 g to 10 g of saccharides and/or aldehydes or their derivatives in solids, 0.1 g to 10 g of sodium and/or kaliumbicarbonate and/or at least one hydroxide from the hydroxides of alkaline metals in solid for each litre of aqueous solution 1% to 40% of hydrogen peroxide. Further can agent contents from 0,1 g to 10 g sodium peroxoborate and/or sodium tetraborate and/or sodium pyrophosphate. This regenerative agent represents a considerable improvement compared to the previous solution. Its advantage is the smooth regeneration of the battery's electrodes.
  • This objective resolves the method of the regeneration of lead battery cells with sulfuric acid electrolytes and alkaline battery cells filled with potassium hydroxide, during which the regeneration additive on the basis of aqueous hydrogen peroxide is added to the electrolyte after which at least one cell or storage battery is charged and discharged in the regular manner.
  • the essence of this invention lies in the fact that at least one cell or storage battery being above the level of the full charge is formed by the cyclical charging and discharging over a total period of 10-70 hours, while at least one cell or storage battery is charged for a period of 15-20 minutes with a current of 1.1%-4% related to the value of the nominal capacity of the cell or storage battery and is discharged for a period of 0.5-2 minutes with a current of 0%-5% related to the nominal value of the capacity of the cell or storage battery.
  • the main advantage of this invention is that with the chemically treated surface layer of the electrodes, with the help of peroxidic compounds on the basis of a hydrogen peroxide solution, various methods are possible to significantly restore the charging above the limit of the basic charging or below the limit of discharging and even improve it above the level attained during its creation.
  • the method of electrochemical regeneration of lead storage batteries filled with a sulfuric acid electrolyte supplemented with a combination of the proposed recharging methods according to the invention increases the effect of regeneration more strikingly and enables the repeated restoration of or increase to the capacity of the battery high above its original nominal value. By extending the life of the cells or storage batteries the amount of dangerous waste is decreased which contributes to the improvement of the ecology.
  • Regeneration in accordance with this invention leads to a perfect surface change to the electrodes, to the softening of its surface, which increases the active functional area of the electrodes on which the size of the capacity of the cell or storage battery depends. For example, with an original battery with a manufacturer's specification of 120 Ah it is possible to increase its nominal value to up to 150 Ah after using the regeneration in accordance with this invention and its life can be extended up to two times.
  • the advantage of regenerating in accordance with this invention is that it is possible to repeat it.
  • the cyclical charging and discharging in a defined time interval with a defined current deformation adjusts the quality of the electrolyte so that the conductive particles are transformed into non-conducting particles, which decreases the self-discharge of the cell or battery.
  • the charging and discharging values are chosen sparingly so that the electrodes are not damaged by, for example, distortion or deformation, because if the plates of the battery are hard, they are damaged at a higher current and its longer effect.
  • the bottom limit of the charging current is chosen so that electrochemical changes do not occur to the cells.
  • the upper limit of the charging current is chosen in order that the cell or storage battery is not overheated during the charging.
  • a higher discharging current than charging current can be used because it acts for a considerably shorter time and its purpose is to lower the compressive voltage between the electrolyte and electrodes of the cells.
  • a zero value of the discharging current means the interruption of the charging during which the battery's voltage returns or approaches the open-circuit voltage.
  • At least one cell or storage battery being located above the level of full charge is formed by the cyclical charging and discharging during a total period of 10-70 hours, while at least one cell or storage battery is cyclically charged for a period of 15-20 minutes and discharged for a period of 0.5-2 minutes in two forming phases, with it being charged with a current of 1.1%-4% and discharged with a current of 0%-5%, related to the value of the nominal capacity of the cell or storage battery in the first phase, while in the second phase the current decreases during charging to 1.1%-3% and during discharging to 0%-4% related to the nominal value of the capacity of the cell or storage battery.
  • the advantage of this invention's method of regeneration, carried out in two phases is the further improvement of the capacity of the cell or storage battery.
  • This type of regeneration has also proven particularly successful with alkaline cells or batteries, such as NiCd types.
  • Two phases of forming the cell or storage battery allows for the utilization of higher charging and discharging currents in the first phase and lower currents in the second phase which is more beneficial for the battery. In the second phase with the lower current, for example, the softer structure of the surface of the electrodes is attained.
  • At least one cell or storage battery is charged with a current of 5%-10% related to the value of the capacity of the battery until the cell or battery is fully charged, and this up to a value of 2.45 V per cell for acid cells or batteries and 1.7 V per cell for alkaline batteries.
  • This charging is used for the case of hardened plates of stational storage batteries with wide-area electrodes. With this, when charging with a higher current without this modification, it can easily be deformed. In practice the frequent distortion and deformation of the hardened electrodes of the cell was witnessed on energy reserve storage batteries. These changes occurred after the discharging of the battery after a power failure with the subsequent charging by an assigned recharger which is usually set to the values of the given manufacturer. Electrodes hardened in this way are usually not functional any more and can not handle the regular current load without interruption.
  • this alternative regeneration consists in the cell or the entire storage battery composed of the cells located under the level of the permitted discharging is formed by the cyclical charging and discharging during which it discharges for a period of 2-10 minutes with a current of 1% to 4% related to the value of the capacity of the battery and is subsequently charged for a period of 1-2 minutes with a current of 3%-10% related to the value of the capacity of the battery and this to a decrease in the voltage to 1.6 V for the cell or any of the battery's cells. Then the battery supplies 10%-15% of its nominal capacity. This entire procedure is repeated 2-5 times.
  • This alternative type of cyclical discharging and charging is suitable for cells for which the discharge limit is decreased to the limit of 1.6 V per cell for acid cells and 0.7 V per cell for alkaline batteries. In its result it has the same effects as forming a battery above the limit of the full recharged cell.
  • This alternative regeneration method according to this invention requires the greater attention and monitoring of the measurement values.
  • the regeneration process according to this invention can be repeated in accordance with the battery operation demands.
  • the regeneration according to this invention is not suitable for the regular recharging of a battery, though it helps with the capacitive equalization of the battery cells with an advantage.
  • the method of charging according to the invention for regenerated batteries can be carried out advantageously with the help of peroxidic compounds created with the help of an aqueous solution of hydrogen peroxide specified, for example, in AO 260591, AO 263221, AO 262274, AO 271768, AO 271814 and AO 272401 so that the battery, after having the regeneration carried out and after the basic process of charging and discharging, preferably with a current with a size of at least 8% of the nominal value of the battery to the full indication of the charged cell or battery to a voltage of 2.45 V per cell for acid cells or batteries and 1.7 V per cell for alkaline batteries.
  • the regenerative agent contains 1 to 70 ml of sulfuric acid with a density of 1 to 1.32 g ⁇ cm ⁇ 3 , 0.1 g to 10 g of saccharides in solids and/or aldehydes or their derivatives, 0.1 g to 10 g of sodium and/or potassium bicarbonate and/or at least one hydroxide from the group of alkali metal hydroxides in solids, or else a mixture containing 0.1 g to 10 g of sodium peroxoborate and/or sodium tetraborate and/or sodium pyrophosphate and also containing 0.1 g to 20 g of bisodium dinaphtylmethane disulfonic acid salt in solids in each liter of aqueous solution 1% to 40% of hydrogen peroxide.
  • the regenerative agent contains 0.5 g to 2 g of bisodium dinaphtylmethane disulfonic acid salt in solids.
  • the regenerative agent may contain 0.1 g to 5 g of a 10% to 50% aqueous solution of oxi-lignin and/or sulfite liquor.
  • the main advantage of this new invention is the significant improvement of regeneration in general and especially with especially-damaged lead batteries by hardened sulfation on the surface of the electrodes, while the regenerative agent contains a combination of bisodium dinaphtylmethane disulfonic acid salt in an acidic solution, it is chemically stable and no other components do not react in it in the presence of hydrogen peroxide.
  • Bisodium dinaphtylmethane disulfonic acid salt is always added in solid form to an acidic solution of hydrogen peroxide with sulfuric acid. While holding to these conditions the bisodium dinaphtylmethane disulfonic acid salt can be added in any order with the remaining components. The most suitable way to add this material is as the last component. It can eventually be added in a mixture of the solids of the other additives.
  • the defined amount of bisodium dinaphtylmethane disulfonic acid salt helps to dissolve the loose flakes and scales from the battery plates.
  • This highly-effective material is suitable for station batteries.
  • Saccharides and/or aldehydes or their derivatives can be added either directly in the solid form of technically pure chemicals or, if it is advantageous, in a solution. Saccharides and/or aldehydes increase the effects of regeneration.
  • Sodium and/or potassium bicarbonate and/or a hydroxide from the group of alkali metals, i.e. sodium hydroxide, potassium hydroxide and lithium hydroxide, represent the effective ingredient in the regenerative agent which significantly increases the quality of the regeneration process.
  • These components can also be added in the solid form of technically pure chemicals or if it is suitable in its suitable solutions. The addition of sulfuric acid acts as a stabilizer of the regeneration solution and the solution would already begin reacting before being added to the battery without it.
  • Peroxoborate, tetraborate and sodium pyrophosphate increases the regeneration effect and slows and regulates the proceeding chemical reaction in the battery which prevents damage to the separators.
  • Peroxoborate, tetraborate and sodium pyrophosphate can also be added as solid materials, technically pure, or if it is appropriate in their suitable solutions.
  • a regenerative agent is specified for the purposes of easily adding it to the cells and it is composed of one liquid component, being from the aqueous solution of hydrogen peroxide and sulfuric acid in which the saccharides and/or aldehydes or their derivatives, the sodium and/or potassium bicarbonate and/or lithium hydroxide, and peroxoborate, tetraborate and sodium pyrophosphate are dissolved or reacted.
  • the regenerative agent is added to the battery's electrolyte either as a concentrate or diluted in accordance with the intention of the regeneration.
  • a diluted regenerative agent maybe even repeatedly, of course in the framework of the lower concentration of the scope of claims of invention.
  • Concentrated solutions are added for the fast implementation of regeneration after which it is possible to form the regenerated battery.
  • a regenerative agent consisting of two components, being an aqueous solution of hydrogen peroxide and sulfuric acid and a solid component made up of saccharides and/or aldehydes or their derivatives, sodium and/or potassium bicarbonate and/or lithium hydroxide, and peroxoborate, tetraborate and sodium pyrophosphate.
  • This battery was regenerated with the regenerative agent in accordance with Czech patent 292 524 so, the regenerative agent was added in two phases at first 30 ml and then 40 ml to each of the cells after the modification of the electrolyte with an interval of 15 minutes.
  • the battery was charged with a current of 30 A until the beginning of the release of gasses and then recharged with a forming current of 5 A for a period of 60 hours. Ninety-two percent of the nominal value was attained.
  • This regenerative agent was prepared from one liter of 35% aqueous solution of hydrogen peroxide, into which 70 ml of sulfuric acid with a density of 1.28 g ⁇ cm ⁇ 3 is added, followed by one ml of 30% aqueous solution of formaldehyde and 2 g of technically pure sodium hydroxide and/or potassium hydroxide.
  • the regeneration solution was mixed and after mixing was prepared for use.
  • the second half of the battery cell was regenerated with the regenerative agent, with the same composition as in the previous example, with the difference that the regenerative agent contained an additional 2 g of bisodium dinaphtylmethane disulfonic acid salt per liter.
  • the regeneration process was the same as in the first half of the cell of this battery, though the nominal capacity attained was 112%.
  • the second half of the storage battery cell were repeatedly charged and formed according to this submitted invention so that it was at first charged to the full charge mark with a current of 11 A for a period of 15 hours. It was subsequently alternately charged and discharged according to this invention so that after 20 minutes of charging with a current of 5 A (3.125% related to the nominal capacity of the battery) it was always discharged for 1 minute with a current of 6 A (3.75% related to the nominal capacity of the battery) and this entire process of charging and discharging was repeated for a period of 20 hours.
  • the battery was further charged so that after 20 minutes of charging with a current of 3 A (1.87% related to the nominal capacity of the battery) it was always discharged for 2 minutes with a current of 4 A (2.5% related to the nominal capacity of the battery) for a period of an additional 24 hours.
  • a preparation for a lead battery is prepared so that first 60 ml of sulfuric acid with a density of 1.24 g ⁇ cm ⁇ 3 is added to one liter of 30% aqueous solution of hydrogen peroxide. Then 10 g of saccharides are added to the resulting solution, i.e. in the form of technically pure glucose, and also 1 g of technically pure sodium bicarbonate and 2 g of bisodium dinaphtylmethane disulfonic acid salt. The combination is mixed until all of the ingredients have dissolved, at which point the regenerative agent is ready to be used.
  • a traction storage battery used 5 years with a nominal voltage of 24 V and a nominal capacity of 400 Ah with a decreased capacity below about 30% Cn was regenerated with the regenerative agent in accordance with this invention.
  • the preparation was added to each of the cells in two phases in 10-minute intervals after the adjustment of the levels of the electrolyte in the battery cells. In each phase 80 ml of the regenerative agent was added. After the calming of the chemical reaction in about 20 minutes the battery was charged with a current of 50 A until the beginning of the release of gasses. Then the battery was formed by recharging with a current of 8 A for a period of 60 hours. The result of the regeneration was a capacity equalization of the battery cells with a capacity of 102% Cn reached after the regeneration.
  • this battery was further regenerated in accordance with the submitted invention by charging and discharging by the level of the standard discharging so that it was discharged with a current of 5 A (1.25% related to the nominal capacity of the battery) so that after each 10 minutes it was charged for 2 minutes with a current of 16 A (4.0% related to the nominal capacity of the battery) to a decrease in the voltage to 1.6 V in the weakest cell. It was possible to follow this process for about 30 minutes. Then the battery was given a charge of 10% capacity and the process of discharging and charging was repeated 3 33 . Then the battery was charged with a current of 16 A to the full charging mark and discharged with a current of 48 A (12% related to the nominal capacity of the battery) for ten minutes and repeatedly recharged with a constant current of 3 A for a period of 18 hours.
  • An OPzS traction storage battery with a nominal voltage of 12 V and a nominal capacity of 280 Ah was put into operation 8 years ago for a period of 12 months and then was stored without the electrolyte which was poured out of it. Due to the long storage the electrode plates were impaired with a coating of irreversible sulfatation forming on them.
  • This battery was stored for 8 years in a non-standard environment and its electrodes were heavily oxidized. After the repeated dosage of the regenerative agent and charging a capacity of 102% Cn was reached with it.
  • This storage battery was regenerated in accordance with this submitted invention in two phases. In the first phase it was charged with a constant current in the magnitude of
  • the battery was alternately charged and discharged according to this invention so that after 20 minutes of charging with a current of 8 A (2.85% related to the nominal capacity of the battery) it was always discharged for 1 minute with a current of 12 A (4.28% related to the nominal capacity of the battery) while this entire cycle of charging and discharging lasted 24 hours.
  • the regenerative agent specified was single-component in the form of an aqueous solution of hydrogen peroxide and sulfuric acid in which the other components had dissolved or reacted.
  • the regenerative agent specified is binary with one component being liquid, the other solid.
  • the liquid component consists of an aqueous solution of hydrogen peroxide and sulfuric acid where 93% to 99% being aqueous hydrogen peroxide with a concentration of 1% to 40% and 1% to 7% being sulfuric acid with a concentration of 1 to 1.32 g ⁇ cm ⁇ 3 .
  • the solid component consists of 20% to 60% solid saccharides and/or aldehyde or their derivatives, 15% to 50% by weight solid sodium bicarbonate and/or potassium carbonate or lithium carbonate and 20% to 60% by weight solid sodium peroxoborate and/or sodium tetraborate and/or sodium diphosphate.
  • the first component also contains 0.3 g-10 g of a 10% to 50% aqueous solution of derivates of oxi-lignin and/or sulfite liquor.
  • the solid component is added to the battery. For each liter of the battery electrolyte 0.3 g to 15 g of a fixed component is added. Then 30 ml to 70 ml of the liquid component is added to each liter of the battery electrolyte in two consecutive batches, creating the regenerative agent directly in the electrolyte.
  • This type of regenerative agent is suitable for all types of lead batteries with sulfuric acid-filled electrolytes.
  • the regenerative agent specified was applied to a J2-72 Ah-24 V station battery with a decreased capacity of 35% of its nominal value so that 12 g of solid regeneration component in powder form, made by mixing 30 g of technically clear glucose, 15 g of sodium bicarbonate and 55 g of sodium peroxoborate, was added to each cell of the battery. After about 10 minutes had passed 15 ml of 35% aqueous solution of hydrogen peroxide was added to each cell stabilized by sulfuric acid i.e. 5 ml of sulfuric acid with a density of 1.28 g ⁇ cm ⁇ 3 for each liter of 35% aqueous solution of hydrogen peroxide. Then the storage battery was repeatedly charged and discharged and was formed in the end with a forming current. During a capacity test the battery tested showed a capacity of 106% its nominal value.
  • This battery was further regenerated in the manner according to this submitted invention as follows.
  • the storage battery was charged with a current of 5.7 A (8% related to the nominal capacity of the battery) until the state of the beginning of the electrodes' intensive releasing of gasses. Then the storage battery was momentarily discharged with a current of 10.8 A (15% related to the nominal capacity of the battery) for a period of 7 minutes. Subsequently the storage battery was recharged in two phases with a constant current of 1.3 A (1.8% related to the nominal capacity of the battery) for a period of 20 hours. Then the battery was shut off for a period of 10 minutes.
  • the battery was recharged with a constant current of 1.5 A (1.5% related to the nominal capacity of the battery) for a period of an additional 40 hours.
  • the final overall capacity of the battery was 114% of its nominal capacity value.
  • the regenerative agent is used in accordance with example 1 with the difference that the aqueous solution of hydrogen peroxide will be 1%-10%.
  • This regenerative agent is suitable for the gradual regeneration during the operation of the battery. Instead of the regular topping-up of the evaporated electrolyte with distilled water this regenerative agent is poured into the battery as needed.
  • the regenerative agent is prepared for lead batteries so that 60 ml of sulfuric acid with a density of 1.28 g ⁇ cm ⁇ 3 is added to 1 liter of 10% aqueous solution of hydrogen peroxide. 5 g of saccharides, i.e. in the form of technically pure glucose, are added to the resulting solution as is 1 g of technically pure sodium bicarbonate. Finally 2 g of bisodium dinaphtylmethane disulfonic acid salt is added.
  • the compound is mixed whereby the regenerative agent is ready to be used.
  • This regenerative agent was used in a lead battery in that after the warranty period of the starting battery 55 Ah-12V had expired the regenerative agent was regularly poured into it over its entire lifetime instead of distilled water.
  • the storage battery in question was used for more than 5 years after the warranty period with good starting capabilities even in low temperatures under minus 20° C.
  • This example demonstrates the regenerative agent used in operations for a starting battery. If it would have been necessary to increase the capacity of such a battery, it is essential to disconnect it from operations for the regeneration and to proceed with the regeneration method in accordance with this invention. In this case the closest regeneration would be, for example, according to example 1, though with about a third of the current levels while maintaining the same charging and discharging periods.
  • a Ni/Cd battery with 5 cells with an original capacity of 160 Ah demonstrated a capacity of 150% of the capacity after charging with a current of 16 A and only 42% of the capacity after discharging with a current of 16 A.
  • the battery was discharged and regenerated in accordance with AO 262 274 with a regenerative agent created with 10 g of non-aqueous sodium borate mixed into 400 ml of 15% hydrogen peroxide which was directly added gradually to the battery. After finishing the reaction lasting about 30 minutes an exchange of the electrolyte in the battery was carried out with a rinsing of the cells with distilled water.
  • the battery was repeatedly charged with a current of 12 A for a period of 10 hours. Subsequently it was alternately charged and discharged in accordance with this submitted invention so that after 20 minutes of charging with a current of 5 A (3.125% related to the nominal capacity of the battery) it was always discharged for 2 minutes with a current of 6 A (3.75% related to the nominal capacity of the battery) and this entire process of charging and discharging was repeated for a period of 20 hours. Then the battery was further charged so that after 20 minutes of charging with a current of 3 A (1.875% related to the nominal capacity of the battery) it was always discharged for 2 minutes with a current of 5 A (3.125% related to the nominal capacity of the battery) for a period of an additional 24 hours.
  • the method of regenerating lead battery cells with a sulfuric acid electrolyte and alkaline battery cells filled with potassium hydroxide is suitable for both the industrial areas of station, lighting, traction and starting storage batteries as well as for personal use for the purpose of the further extension of the life of the cells or the entire batteries.
  • the claimed regenerative agent is suitable for all types of lead batteries with a sulfuric acid filling.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
US10/548,468 2003-03-10 2004-03-10 Method of regenerating lead battery cells and regenerative agent for performing of this method Abandoned US20060145664A1 (en)

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CZ2003699A CZ2003699A3 (en) 2003-03-10 2003-03-10 Regenerating composition for lead-acid batteries
CZPV2003-699 2003-03-10
CZ20031205A CZ20031205A3 (cs) 2003-04-30 2003-04-30 Způsob regenerace akumulátorových článků
CZPV2003-1205 2003-04-30
PCT/CZ2004/000013 WO2004082038A2 (en) 2003-03-10 2004-03-10 Method of regenerating battery cells and regenerative agent for lead batteries

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DE (1) DE602004029147D1 (ru)
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CN101276944B (zh) * 2008-05-12 2010-06-16 绿源投资控股集团有限公司 一种带电能回收的蓄电池修复系统及其方法
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CN103427125B (zh) * 2012-05-15 2016-04-13 清华大学 硫基聚合物锂离子电池的循环方法
CN103151568A (zh) * 2013-03-16 2013-06-12 蒋菊生 一种电池修复方法
CN103490105A (zh) * 2013-09-28 2014-01-01 德清创诺尔新材料科技有限公司 一种修复内部损坏的移动电源的方法
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PL1611626T3 (pl) 2011-06-30
AU2004219565A1 (en) 2004-09-23
US7750603B2 (en) 2010-07-06
EP1611626B1 (en) 2010-09-15
WO2004082038A2 (en) 2004-09-23
RU2005131966A (ru) 2006-07-10
CN1784800A (zh) 2006-06-07
ATE481755T1 (de) 2010-10-15
WO2004082038A3 (en) 2005-11-10
US20090140695A1 (en) 2009-06-04
CA2518628A1 (en) 2004-09-23
DE602004029147D1 (de) 2010-10-28
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CN100511780C (zh) 2009-07-08
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