WO2004082038A2 - Method of regenerating battery cells and regenerative agent for lead batteries - Google Patents
Method of regenerating battery cells and regenerative agent for lead batteries Download PDFInfo
- Publication number
- WO2004082038A2 WO2004082038A2 PCT/CZ2004/000013 CZ2004000013W WO2004082038A2 WO 2004082038 A2 WO2004082038 A2 WO 2004082038A2 CZ 2004000013 W CZ2004000013 W CZ 2004000013W WO 2004082038 A2 WO2004082038 A2 WO 2004082038A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- battery
- cell
- current
- capacity
- storage battery
- Prior art date
Links
- 230000001172 regenerating effect Effects 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 43
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 73
- 238000007600 charging Methods 0.000 claims abstract description 67
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000011069 regeneration method Methods 0.000 claims abstract description 58
- 230000008929 regeneration Effects 0.000 claims abstract description 55
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 53
- 238000007599 discharging Methods 0.000 claims abstract description 39
- 239000007864 aqueous solution Substances 0.000 claims abstract description 29
- 239000007787 solid Substances 0.000 claims abstract description 26
- 239000002253 acid Substances 0.000 claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- 150000001720 carbohydrates Chemical class 0.000 claims abstract description 15
- 239000000654 additive Substances 0.000 claims abstract description 14
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 13
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims abstract description 12
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 11
- 229940048086 sodium pyrophosphate Drugs 0.000 claims abstract description 11
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims abstract description 11
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims abstract description 11
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 9
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 8
- GDTSJMKGXGJFGQ-UHFFFAOYSA-N 3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B([O-])OB2OB([O-])OB1O2 GDTSJMKGXGJFGQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000007423 decrease Effects 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims abstract description 6
- 235000015497 potassium bicarbonate Nutrition 0.000 claims abstract description 6
- 239000011736 potassium bicarbonate Substances 0.000 claims abstract description 6
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 3
- 239000003792 electrolyte Substances 0.000 claims description 34
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- 230000000996 additive effect Effects 0.000 claims description 9
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 claims description 8
- 229910021538 borax Inorganic materials 0.000 claims description 7
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 7
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 claims description 6
- 239000004328 sodium tetraborate Substances 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 4
- 229920005610 lignin Polymers 0.000 claims description 4
- 150000004679 hydroxides Chemical class 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 12
- 239000000243 solution Substances 0.000 description 17
- 230000008569 process Effects 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 230000002427 irreversible effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000003247 decreasing effect Effects 0.000 description 6
- 230000006872 improvement Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000008103 glucose Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- -1 peroxide compounds Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000003929 acidic solution Substances 0.000 description 2
- 230000001914 calming effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000001177 diphosphate Substances 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- 229910005580 NiCd Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001447 compensatory effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010278 pulse charging Methods 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/24—Alkaline accumulators
- H01M10/30—Nickel accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0005—Acid electrolytes
- H01M2300/0011—Sulfuric acid-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0014—Alkaline electrolytes
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling 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 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.
- 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.
- 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.
- 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 dinaphtyimethane 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.
- 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.
- 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.
- AO 260591 , AO 263221 , AO 262274, AO 271768, AO 271814 and AO 272401 so that the battery, after having the regenerati oi n carried out and after the basic process of charging and discharging, preferably wi tlh a current with a size of at least 8% of the nominal value of the battery to the full ndication 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 dinaphtyimethane 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 dinaphtyimethane 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 sulfaflon on the surface of the electrodes, while the regenerative agent contains a combination of bisodium dinaphtyimethane 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.
- the defined amount of bisodium dinaphtyimethane disulfonic acid salt helps to dissolve the loose flakes and scales from the battery plates.
- This highly-effective material is suitable for station batteries.
- Peroxoborate, tetraborate and sodium pyrophosphate can also be added as solid materials, technically pure, or if it is appropriate in their suitable solutions.
- Concentrated solutions are added for the fast implementation of regeneration after which it is possible to form the regenerated battery.
- a regenerative agent is specified, 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 2g of bisodium dinaphtyimethane 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%.
- This second half of the cell was further regenerated according to this submitted invention in the following manner:
- 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 dinaphtyimethane 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 3x. 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 regenerated with the following regenerative agent made with 10 g of technically pure sodium bicarbonate, 70 ml of sulfuric acid with a density of 1.28 g.cm "3 , 5g of saccharides in the form of solid glucose and 5 g of technically pure sodium tetraborate added to 1 liter of 30% aqueous solution of hydrogen peroxide.
- the sodium tetraborate can be fully or partially replaced by diphosphate.
- 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.
- the first phase it was charged with a constant current in the magnitude of 4.5 A (1.6% related to the nominal capacity of the battery).
- a recharger from the Czech company Condata was used with a special recharging with a negative impulse for a period of 20 hours in which the first phase of regeneration according to the submitted invention is completed.
- the battery was discharged with a current of 50 A (17.85 % related to the nominal capacity of the battery).
- 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 0.3g - 10g 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 dinaphtyimethane 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.
- An alkaline Ni/Cd battery of unknown age was regenerated with the regenerative agent in accordance with Czechoslovak Author's Certificate no. AO 262 274 in the following manner.
- 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.
- 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 result was an increase of the battery's capacity to 102 % of its nominal capacity value.
- 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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- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
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- Electrochemistry (AREA)
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Abstract
Description
Claims
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA 2518628 CA2518628C (en) | 2003-03-10 | 2004-03-10 | Method of regenerating lead battery cells and regenerative agent for performing this method |
AT04718901T ATE481755T1 (en) | 2003-03-10 | 2004-03-10 | METHOD FOR REGENERATING BATTERY CELLS AND REGENERATING AGENT FOR LEAD BATTERIES |
PL04718901T PL1611626T3 (en) | 2003-03-10 | 2004-03-10 | Method of regenerating battery cells and regenerative agent for lead batteries |
US10/548,468 US20060145664A1 (en) | 2003-03-10 | 2004-03-10 | Method of regenerating lead battery cells and regenerative agent for performing of this method |
DE200460029147 DE602004029147D1 (en) | 2003-03-10 | 2004-03-10 | METHOD FOR THE REGENERATION OF BATTERY CELLS AND REGENERATING AGENTS FOR LEAD TREATMENT |
EP20040718901 EP1611626B9 (en) | 2003-03-10 | 2004-03-10 | Method of regenerating battery cells and regenerative agent for lead batteries |
AU2004219565A AU2004219565B2 (en) | 2003-03-10 | 2004-03-10 | Method of regenerating battery cells and regenerative agent for lead batteries |
CNB2004800126555A CN100511780C (en) | 2003-03-10 | 2004-03-10 | Method of regenerating battery cells and regenerative agent for the method |
IL17073405A IL170734A (en) | 2003-03-10 | 2005-09-07 | Method of regenerating lead battery cells and regenerative agent for performing this method |
US12/318,088 US7750603B2 (en) | 2003-03-10 | 2008-12-22 | Method of regenerating lead battery cells and regenerative agent for performing of this method |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CZ2003699A CZ2003699A3 (en) | 2003-03-10 | 2003-03-10 | Regenerating composition for lead-acid batteries |
CZPV2003-699 | 2003-03-10 | ||
CZ20031205A CZ20031205A3 (en) | 2003-04-30 | 2003-04-30 | Regeneration process of accumulator cells |
CZPV2003-1205 | 2003-04-30 |
Publications (2)
Publication Number | Publication Date |
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WO2004082038A2 true WO2004082038A2 (en) | 2004-09-23 |
WO2004082038A3 WO2004082038A3 (en) | 2005-11-10 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/CZ2004/000013 WO2004082038A2 (en) | 2003-03-10 | 2004-03-10 | Method of regenerating battery cells and regenerative agent for lead batteries |
Country Status (11)
Country | Link |
---|---|
US (2) | US20060145664A1 (en) |
EP (1) | EP1611626B9 (en) |
CN (1) | CN100511780C (en) |
AT (1) | ATE481755T1 (en) |
AU (1) | AU2004219565B2 (en) |
CA (1) | CA2518628C (en) |
DE (1) | DE602004029147D1 (en) |
IL (1) | IL170734A (en) |
PL (1) | PL1611626T3 (en) |
RU (1) | RU2320054C2 (en) |
WO (1) | WO2004082038A2 (en) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
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CN100384010C (en) * | 2006-06-16 | 2008-04-23 | 果崇贤 | Method for prolonging service life of accumulator |
CN101276944B (en) * | 2008-05-12 | 2010-06-16 | 绿源投资控股集团有限公司 | Accumulator repairing system and method with function of recovering electric energy |
CN102013534B (en) * | 2010-11-05 | 2013-05-08 | 江西省电力科学研究院 | Cathode protection-based valve control type lead-acid battery capacity activation solution |
EP2764601A4 (en) * | 2011-10-03 | 2015-05-06 | Megapulse Australia Pty Ltd | An improved battery conditioning apparatus |
CN103427125B (en) * | 2012-05-15 | 2016-04-13 | 清华大学 | The round-robin method of sulfenyl polymer Li-ion battery |
CN103151568A (en) * | 2013-03-16 | 2013-06-12 | 蒋菊生 | Battery repairing method |
CN103490105A (en) * | 2013-09-28 | 2014-01-01 | 德清创诺尔新材料科技有限公司 | Method for repairing internally-damaged mobile power supply |
CN108417866B (en) * | 2018-01-31 | 2020-10-09 | 浩发环保科技(深圳)有限公司 | Lead methanesulfonate electrolyte reduction regenerant and lead methanesulfonate electrolyte reduction regeneration method |
CN113258159B (en) * | 2021-05-06 | 2022-07-15 | 哈尔滨工程大学 | Device and method for regenerating lithium ion battery electrode material |
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- 2004-03-10 CA CA 2518628 patent/CA2518628C/en not_active Expired - Fee Related
- 2004-03-10 WO PCT/CZ2004/000013 patent/WO2004082038A2/en active IP Right Grant
- 2004-03-10 PL PL04718901T patent/PL1611626T3/en unknown
- 2004-03-10 CN CNB2004800126555A patent/CN100511780C/en not_active Expired - Fee Related
- 2004-03-10 EP EP20040718901 patent/EP1611626B9/en not_active Expired - Lifetime
- 2004-03-10 US US10/548,468 patent/US20060145664A1/en not_active Abandoned
- 2004-03-10 DE DE200460029147 patent/DE602004029147D1/en not_active Expired - Lifetime
- 2004-03-10 RU RU2005131966A patent/RU2320054C2/en not_active IP Right Cessation
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2005
- 2005-09-07 IL IL17073405A patent/IL170734A/en not_active IP Right Cessation
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Also Published As
Publication number | Publication date |
---|---|
CA2518628C (en) | 2013-05-14 |
IL170734A (en) | 2012-04-30 |
US20060145664A1 (en) | 2006-07-06 |
AU2004219565A1 (en) | 2004-09-23 |
EP1611626B9 (en) | 2011-03-02 |
RU2005131966A (en) | 2006-07-10 |
DE602004029147D1 (en) | 2010-10-28 |
US7750603B2 (en) | 2010-07-06 |
CN100511780C (en) | 2009-07-08 |
AU2004219565B2 (en) | 2006-07-13 |
PL1611626T3 (en) | 2011-06-30 |
EP1611626A2 (en) | 2006-01-04 |
RU2320054C2 (en) | 2008-03-20 |
WO2004082038A3 (en) | 2005-11-10 |
CN1784800A (en) | 2006-06-07 |
EP1611626B1 (en) | 2010-09-15 |
ATE481755T1 (en) | 2010-10-15 |
US20090140695A1 (en) | 2009-06-04 |
CA2518628A1 (en) | 2004-09-23 |
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