CN116799328A - Electrolyte for lead storage battery - Google Patents
Electrolyte for lead storage battery Download PDFInfo
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- CN116799328A CN116799328A CN202310947052.9A CN202310947052A CN116799328A CN 116799328 A CN116799328 A CN 116799328A CN 202310947052 A CN202310947052 A CN 202310947052A CN 116799328 A CN116799328 A CN 116799328A
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- Prior art keywords
- electrolyte
- storage battery
- lead storage
- sodium tetraborate
- sulfate
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 47
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims abstract description 34
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 32
- 229910021538 borax Inorganic materials 0.000 claims abstract description 31
- 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 abstract description 31
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 31
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 27
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 27
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 27
- 239000000654 additive Substances 0.000 claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 76
- 238000003756 stirring Methods 0.000 claims description 34
- -1 octyl sulfonic acid amine Chemical class 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 10
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 9
- HNGDCKBWRHWCMU-UHFFFAOYSA-N N,N,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-nonadecafluorooctan-1-amine Chemical compound FN(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F HNGDCKBWRHWCMU-UHFFFAOYSA-N 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 5
- 229940103272 aluminum potassium sulfate Drugs 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 12
- 238000005260 corrosion Methods 0.000 abstract description 12
- 230000019635 sulfation Effects 0.000 abstract description 7
- 238000005670 sulfation reaction Methods 0.000 abstract description 7
- QTKKZNYORNDROP-UHFFFAOYSA-N trifluoro(1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctyl)azanium Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)[N+](F)(F)F QTKKZNYORNDROP-UHFFFAOYSA-N 0.000 abstract description 5
- 230000002035 prolonged effect Effects 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 230000005496 eutectics Effects 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 239000013078 crystal Substances 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000007600 charging Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000012795 verification Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002000 Electrolyte additive Substances 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- RADKZDMFGJYCBB-UHFFFAOYSA-N Pyridoxal Chemical compound CC1=NC=C(CO)C(C=O)=C1O RADKZDMFGJYCBB-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- CDMADVZSLOHIFP-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;decahydrate Chemical group O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 CDMADVZSLOHIFP-UHFFFAOYSA-N 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 125000005007 perfluorooctyl group Chemical group FC(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229960003581 pyridoxal Drugs 0.000 description 1
- 235000008164 pyridoxal Nutrition 0.000 description 1
- 239000011674 pyridoxal Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000019794 sodium silicate Nutrition 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000010200 validation analysis Methods 0.000 description 1
- 229910006529 α-PbO Inorganic materials 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
- H01M10/08—Selection of materials as electrolytes
-
- 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
- H01M10/42—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
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0005—Acid electrolytes
- H01M2300/0011—Sulfuric acid-based
Landscapes
- 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)
Abstract
The invention discloses an electrolyte for a lead storage battery, and belongs to the technical field of lead storage batteries. The invention adopts potassium sulfate, aluminum sulfate, sodium tetraborate and perfluorooctyl ammonium sulfonate as additives to be added into electrolyte for the lead storage battery, and the phenomena of positive grid corrosion, negative sulfation and the like are restrained by the eutectic action of the potassium sulfate and the aluminum sulfate, the buffer action of the sodium tetraborate and the adsorption action of the perfluorooctyl ammonium sulfonate in a synergistic way, so that the lead storage battery is prolonged.
Description
Technical Field
The invention belongs to the technical field of lead storage batteries, and particularly relates to an electrolyte for a lead storage battery.
Background
Since the advent of lead storage batteries, the lead storage batteries have been dominant in the secondary battery field by virtue of the advantages of stable performance, low price, high resource recycling rate and the like in a long period of half century, and have a very wide application range, and cover various fields such as starting, power, energy storage and the like. However, lead storage batteries themselves suffer from disadvantages such as low energy density, relatively poor life performance, and the like. At present, with the rapid rise of high-performance novel energy sources represented by lithium batteries, part of application fields of lead storage batteries are gradually replaced. Nevertheless, lead storage batteries must continue to play an important role in the future for a considerable period of time, particularly in the low-speed electric automobiles and electric bicycle power fields. The traditional lead storage battery for power has the problems of early capacity attenuation, short cycle service life and the like, and the failure mode of the lead storage battery is mainly represented by positive grid corrosion, positive active material softening and falling, negative sulfation and the like. The positive grid corrosion occurs in the whole process of plate solidification, battery formation and recycling, and comprises solid-phase reaction and liquid-phase reaction. After recycling, a thicker corrosion layer is generated, the corrosion layer exists in the form of lead sulfate and non-metered lead oxide, and the corrosion layer structurally comprises various defects to generate multidirectional cracks. The growth of the corrosion layer causes a rapid increase in interface or internal resistance, which is a major factor affecting the cycle life of the lead storage battery. The positive electrode active material is softened and falls off due to interface passivation, consumption of alpha-PbO 2 and the like, and the evolution of the positive electrode active material is influenced by a plurality of factors such as sulfuric acid concentration, electrolyte layering, operating environment temperature and the like. Negative electrode sulfation should be strictly referred to as negative electrode irreversible sulfation. Under normal conditions, lead storage batteries form lead sulfate crystals when discharged and can be reduced to lead relatively easily when charged. However, if the battery is frequently in an undercharged or overdischarged state due to improper use and maintenance, the negative electrode gradually forms a coarse and hard lead sulfate, which is hardly dissolved, and it is difficult to convert it into an active material again by charging in a conventional manner. This directly results in a decrease in battery capacity until the battery life is prematurely terminated.
The invention patent of the patent No. CN103268966B reports an electrolyte additive for prolonging the service life of the lead-calcium battery, and the electrolyte is compounded with organosilane, phosphoric acid, mannitol, polyoxyethylene ether, organic silicone oil and polyacrylamide, so that the cycle life of the lead-acid battery can be effectively prolonged by more than 50%.
The patent number CN1170396C discloses a lead-acid storage battery electrolyte, which comprises carbon, sodium sulfate, magnesium sulfate, sodium silicate, sodium acetate, cobalt acetate, phosphoric acid, 2, 6-di-tert-butyl p-cresol and pyridoxal 2, 5-phosphate.
However, the lead storage battery of the above prior art electrolyte formulation still has a short cycle life.
Disclosure of Invention
The invention aims to solve the technical problem of providing an electrolyte for a lead-acid storage battery, which is prepared by adding potassium sulfate, aluminum sulfate, sodium tetraborate and perfluoro octyl sulfonic acid amine into the electrolyte according to a certain mass percent, and inhibiting the phenomena of positive grid corrosion, negative sulfation and the like by virtue of the eutectic action of the potassium sulfate and the aluminum sulfate, the buffer action of the sodium tetraborate and the adsorption action of the perfluoro octyl sulfonic acid amine, so that the cycle life of the lead-acid storage battery, especially the lead-acid storage battery for an electric bicycle is prolonged.
The specific technical scheme of the invention is as follows:
the electrolyte for the lead storage battery comprises sulfuric acid solution and additives, wherein the additives comprise the following components in percentage by mass based on the total electrolyte: 0.2 to 2 percent of potassium sulfate, 0.2 to 2 percent of aluminum sulfate, 0.2 to 2 percent of sodium tetraborate and 0.001 to 0.01 percent of perfluor octyl sulfonic acid amine.
Besides the aqueous solution of sulfuric acid, sodium tetraborate is used for replacing sodium sulfate, so that the electrolyte can not only play a role in buffering sodium sulfate, but also relieve grid corrosion caused by sodium sulfate, and in addition, potassium sulfate, aluminum sulfate and perfluoro octyl ammonium sulfonate are added.
The potassium sulfate is colorless transparent crystal powder, the aluminum sulfate is aluminum sulfate octadecatriend, and the property is white powder.
In the charging process of the battery, potassium sulfate and aluminum sulfate are deposited on the negative plate together with Pb to form mixed crystals, and the mixed crystals are embedded in lead lattices. During discharge, potassium and aluminum are first oxidized into ions by the oxide layer to enter the solution, so that vacancies are left in crystal lattices, and continuous coarse crystals cannot be formed on the surface of the electrode, so that sulfation is avoided, the internal resistance of the battery is reduced, and the electrochemical performance of the battery is greatly improved. Meanwhile, fine and compact lead sulfate is prevented from being formed, and further shrinkage failure of the negative plate is prevented. In addition, potassium sulfate improves the oxygen evolution overpotential of the positive electrode, promotes the charging reaction and improves the charging efficiency. Aluminum sulfate increases the water content of the active material gel region, facilitating the formation of amorphous and hydrated PbO 2 . The particle size is thinned, and the bonding area and bonding strength between active substances are increased.
The sodium tetraborate is sodium tetraborate decahydrate and is colorless transparent crystal powder.
Sodium tetraborate is decomposed into sodium ions in sulfuric acid and borate ions, wherein the sodium ions can play a role in preventing dendrite short circuit of the traditional sodium sulfate additive to increase conductivity, and the borate ions relieve corrosion of the positive grid due to weak acid performance. Meanwhile, the method also has the effects of refining grains and reducing self-discharge.
The perfluorinated octyl sulfonic acid amine is colorless powder, and the content is more than or equal to 95%.
The perfluoro octyl sulfonic acid amine is an anionic surfactant and can be used for discharging with Pb by adsorption 2+ Ion forming 'lead-sulfonate' composite intermediate to prevent formation of compact lead sulfate layer on the surface of base metal and change PbO during charging 2 The crystal form is smaller in particle size and higher in porosity, and the surface area of the electrode is enlarged, so that the utilization rate of the positive electrode active material is improved, and the battery capacity is further improved.
Preferably, the additive comprises the following components in percentage by mass based on the total electrolyte: 0.5 to 1.5 percent of potassium sulfate, 0.5 to 1.5 percent of aluminum sulfate, 0.8 to 1.2 percent of sodium tetraborate and 0.002 to 0.008 percent of perfluor octyl sulfonic acid amine.
More preferably, the additive comprises the following components in percentage by mass based on the total electrolyte: potassium sulfate 0.5%, aluminum sulfate 1.5%, sodium tetraborate 0.8%, and perfluorooctyl sulfonic acid amine 0.008%;
or the additive comprises the following components in percentage by mass of the total electrolyte: 1.5% of potassium sulfate, 0.5% of aluminum sulfate, 1.2% of sodium tetraborate and 0.002% of perfluorooctyl sulfonic acid amine.
The density of the sulfuric acid solution is 1.245g/cm 3 。
The invention also provides a preparation method of the electrolyte for the lead storage battery, which comprises the steps of sequentially adding sodium tetraborate, aluminum sulfate, potassium sulfate and perfluor octyl amine sulfonate into a sulfuric acid solution, and continuously stirring in the adding process. Preferably, sodium tetraborate, aluminum sulfate, potassium sulfate and perfluorooctyl amine sulfonate are added to the sulfuric acid solution in sequence, and after the former is completely dissolved, the next is added.
The invention also provides a lead storage battery, which comprises the electrolyte and is used for the lead storage battery. The lead storage battery is used for an electric bicycle.
The invention has the beneficial effects that:
the invention adopts potassium sulfate, aluminum sulfate, sodium tetraborate and perfluorooctyl ammonium sulfonate as additives to be added into electrolyte for the lead storage battery, and the phenomena of positive grid corrosion, negative sulfation and the like are restrained by the eutectic action of the potassium sulfate and the aluminum sulfate, the buffer action of the sodium tetraborate and the adsorption action of the perfluorooctyl ammonium sulfonate in a synergistic way, so that the lead storage battery is prolonged.
Drawings
Fig. 1 is a graph showing the cycle performance of the battery prepared from the electrolyte of comparative example 1.
Fig. 2 is a graph showing the cycle performance of the battery prepared from the electrolyte of comparative example 2.
Fig. 3 is a graph showing the cycle performance of the battery prepared from the electrolyte of comparative example 3.
FIG. 4 is a graph showing the cycle performance of the batteries prepared by the electrolytes of examples 1 and 2 compared with that of a conventional battery (the conventional battery in the present patent refers to a battery in which anhydrous sodium sulfate is added in an electrolyte of 0.8% by mass, and the same applies to the following).
Detailed Description
Example 1
At 25 ℃, the density is 1.4g/cm 3 Is prepared by adding sulfuric acid into water by a container, stirring thoroughly with stirring paddle until sulfuric acid is distributed uniformly to obtain 33.5% (density about 1.245 g/cm) 3 ) Is a sulfuric acid solution of (a). Then, 800g of sodium tetraborate was added while stirring until all of it was dissolved. Then, 1500g of aluminum sulfate was added while stirring until it was completely dissolved. Then 500g of potassium sulfate was added with stirring until it was completely dissolved. Then 8g of perfluorooctyl sulfonic acid amine was added with stirring until it was completely dissolved. The electrolyte for the lead storage battery is obtained.
Example 2
At 25 ℃, the density is 1.4g/cm 3 Is prepared by adding sulfuric acid (63.9 kg) into water, collecting pure water (32.9 kg), and stirring thoroughly with stirring paddle until the sulfuric acid is distributed uniformly to obtain solid content of 33.5% (density about 1.245 g/cm) 3 ) Is a sulfuric acid solution of (a). Then, 1200g of sodium tetraborate was added with stirring until all of it was dissolved. Then, 500g of aluminum sulfate was added while stirring until it was completely dissolved. 1500g of potassium sulfate was then added with stirring until it was completely dissolved. 2g of perfluorooctyl sulfonic acid amine was then added with stirring until all of it was dissolved. The electrolyte for the lead storage battery is obtained.
Example 3
At 25 ℃, the density is 1.4g/cm 3 The sulfuric acid 58.7kg, pure water 40.7kg, adding sulfuric acid into water, stirring thoroughly with stirring paddle until the sulfuric acid is distributed uniformly, obtaining solid content of 30.0% (density about 1.215 g/cm) 3 ) Is a sulfuric acid solution of (a). Then, 200g of sodium tetraborate was added with stirring until all of it was dissolved. Then, 200g of aluminum sulfate was added while stirring until it was completely dissolved. 200g of potassium sulfate was then added with stirring until it was completely dissolved. 1g of perfluorooctyl sulfonic acid amine was then added with stirring until it was completely dissolved. The electrolyte for the lead storage battery is obtained.
Example 4
At 25 ℃, the density is 1.4g/cm 3 Is prepared by adding sulfuric acid into water by a container, adding sulfuric acid of 29.2kg pure water into the water, and stirring thoroughly with stirring paddle until the sulfuric acid is distributed uniformly to obtain solid content of 35.0% (density about 1.256 g/cm) 3 ) Is a sulfuric acid solution of (a). Then, 2000g of sodium tetraborate was added with stirring until all of it was dissolved. Then, 2000g of aluminum sulfate was added while stirring until it was completely dissolved. 2000g of potassium sulfate were then added with stirring until all of it had dissolved. 10g of perfluorooctyl sulfonic acid amine was then added with stirring until all of it was dissolved. The electrolyte for the lead storage battery is obtained.
Comparative example 1
And (3) aluminum sulfate single factor verification: aluminum sulfate in various amounts (1.0, 2.0, 2.5, 3.75, 5.0, 6.25 wt.%) was added. The preparation method of the electrolyte added with aluminum sulfate comprises the following steps: at 25 ℃, the density is 1.4g/cm respectively 3 65.3kg,64.7kg,64.3kg,63.5kg,62.7kg,61.9kg of pure water, 33.7kg,33.3kg,33.2kg,32.7kg,32.3kg,31.9kg of sulfuric acid, respectively, are added into water by taking containers, and are fully stirred by stirring paddles until the sulfuric acid is uniformly distributed, thereby obtaining six groups of sulfuric acid with solid contents of 33.5% (the density is about 1.245 g/cm) 3 ) Is a sulfuric acid solution of (a). Then 1000g,2000g,2500g,3750g,5000g and 6250g of aluminum sulfate were added to the six groups of sulfuric acid solutions, respectively, while stirring, until all of them were dissolved. The electrolyte for the lead storage battery is obtained.
Comparative example 2
Single factor validation of sodium tetraborate: sodium tetraborate in different addition amounts (0.8, 1.2, 1.6, 2.0 wt.%). The preparation method of the electrolyte added with sodium tetraborate comprises the following steps: at 25 ℃, the density is 1.4g/cm respectively 3 The sulfuric acid of (2) is added into water by taking 33.7kg,33.6kg,33.5kg and 33.3kg of pure water respectively, taking containers respectively, fully stirring the mixture by using a stirring paddle until the sulfuric acid is uniformly distributed, and obtaining four groups of solid contents of 33.5% (the density is about 1.245 g/cm) 3 ) Is a sulfuric acid solution of (a). Then, 800g,1200g,160 g and 2000g of sodium tetraborate are added to the four groups of sulfuric acid solutions respectively under stirring until all of them are dissolved. The electrolyte for the lead storage battery is obtained.
Comparative example 3
Perfluor octyl amine sulfonate single factor verification: different amounts (0.002, 0.004, 0.008, 0.016 wt.%) of perfluorooctyl amine sulfonate. The preparation method of the electrolyte added with perfluorooctyl sulfonic acid amine comprises the following steps: at 25 ℃, the density is 1.4g/cm respectively 3 Respectively taking 34kg of pure water and 34kg of pure water, respectively taking a container, adding sulfuric acid into water, and fully stirring by a stirring paddle until the sulfuric acid is uniformly distributed to obtain four groups with 33.5% of solid content (density is about 1.245 g/cm) 3 ) Is a sulfuric acid solution of (a). Then, 2g,4g,8g and 16g of perfluorooctyl amine sulfonate were added to each of the four groups of sulfuric acid solutions while stirring until all of them were dissolved. The electrolyte for the lead storage battery is obtained.
Test example 1
The electrolytes prepared in examples 1 to 2 and comparative examples 1 to 3 were assembled into a 6-EVF-20 (12V 20 Ah) battery, and then subjected to cycle performance test under the following conditions:
1) 10A discharged until the cell terminal voltage drops to 10.5V;
2) Constant current charging is carried out until the voltage of the battery terminal reaches 14.8V;
3) Turning to constant voltage charging, and stopping charging when the total time of constant current charging and constant voltage charging reaches 4.25 hours;
4) Standing for 0.5 hours.
The above steps 1) to 4) are repeated as a cycle, and when the capacity is reduced to less than 80% of the initial capacity, the battery life is terminated, and the battery life is represented by the number of cycles. The test results are shown in FIGS. 1 to 4.
As shown in fig. 1, the aluminum sulfate single factor verification was performed on a 6-EVF-20 (12 v20 ah) electric bicycle battery, and the expected effect was not obtained, with 9 to 98 cycles less than the conventional battery. And when the addition amount exceeds 2.0wt.%, the cycle life becomes worse as the aluminum sulfate content increases.
As shown in fig. 2, the single factor test result of sodium tetraborate also did not achieve the positive effect, and the cycle times were 3 to 8 times less than those of the conventional battery. And when the content exceeds 2.0wt.%, corrosion of the grid is greatly increased.
As shown in fig. 3, it was found through the verification of perfluorooctyl amine sulfonate that perfluorooctyl amine sulfonate failed to improve the cycle performance of the battery, and the cycle times were 5 to 21 times less than that of the conventional battery. However, perfluorooctyl sulfonic acid amine can improve the initial capacity of the battery to some extent.
As shown in fig. 4, the conventional battery with 0.8% anhydrous sodium sulfate added thereto had a cycle life of 253 times, the battery of example 1 with potassium sulfate, aluminum sulfate, sodium tetraborate and perfluorooctyl sulfonic amine added thereto had a cycle life of 293 times, a cycle life of 15.8% increased, the battery of example 2 had a cycle life of 299 times, and a cycle life increased by 18.2%. In general, the electrolyte additive can improve the cycle life of the battery by more than 15%, has remarkable effect, and has great significance for prolonging the service life of the lead-acid storage battery and improving the competitiveness.
Claims (8)
1. The electrolyte for the lead storage battery comprises sulfuric acid solution and additives, and is characterized in that the additives comprise the following components in percentage by mass based on the total electrolyte: 0.2 to 2 percent of potassium sulfate, 0.2 to 2 percent of aluminum sulfate, 0.2 to 2 percent of sodium tetraborate and 0.001 to 0.01 percent of perfluor octyl sulfonic acid amine.
2. The electrolyte for a lead storage battery according to claim 1, wherein the additive comprises the following components in mass ratio based on the total electrolyte: 0.5 to 1.5 percent of potassium sulfate, 0.5 to 1.5 percent of aluminum sulfate, 0.8 to 1.2 percent of sodium tetraborate and 0.002 to 0.008 percent of perfluor octyl sulfonic acid amine.
3. The electrolyte for a lead storage battery according to claim 2, wherein the additive comprises the following components in mass ratio based on the total electrolyte: potassium sulfate 0.5%, aluminum sulfate 1.5%, sodium tetraborate 0.8%, and perfluorooctyl sulfonic acid amine 0.008%;
or the additive comprises the following components in percentage by mass of the total electrolyte: 1.5% of potassium sulfate, 0.5% of aluminum sulfate, 1.2% of sodium tetraborate and 0.002% of perfluorooctyl sulfonic acid amine.
4. The electrolyte for lead storage battery according to claim 1, wherein the sulfuric acid solution has a density of 1.215 to 1.256g/cm 3 。
5. The method for producing an electrolyte for a lead acid storage battery according to any one of claims 1 to 4, wherein sodium tetraborate, aluminum sulfate, potassium sulfate and perfluorooctyl amine sulfonate are added to a sulfuric acid solution in this order, and stirring is continued during the addition.
6. The process according to claim 5, wherein sodium tetraborate, aluminum sulfate, potassium sulfate and perfluorooctyl amine sulfonate are added to the sulfuric acid solution in this order, and the former is completely dissolved and then the next is added.
7. A lead acid battery comprising an electrolyte, wherein the electrolyte for a lead acid battery according to any one of claims 1 to 4 is used.
8. The lead storage battery according to claim 7, wherein the lead storage battery is used for an electric bicycle.
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