Additive for sulfuric-acid electrolyte and method of use of such additive

FIELD: electrical engineering; chemical current sources; production of lead-acid cells, additives for sulfuric-acid electrolytes in particular.

SUBSTANCE: proposed additive is made from mixture of sulfate of metal with phosphonocarboxylic acids and aminoalkylphosphonic or hydroxyalkylene diphosphonous acids in diluted sulfuric-acid medium at pH no more than 0.8 and total content of phosphonous acids equal to 0.001-0.015 mass-% and metal sulfate of 10-18 mass-%. Additive may additionally include fluorine-containing surfactants in the amount of 0.01-0.1 mass-%. Proposed additive is used for excluding sulfitation of plates of lead-acid cells and restoration of sulfated storage batteries.

EFFECT: enhanced efficiency.

5 cl, 3 ex

 

The invention relates to the field of electrical engineering, namely to chemical current sources, and can be used in the manufacture of lead acid batteries, in particular, in the production of additives for sulfuric acid electrolytes.

Lead acid batteries are the most widely used in automotive batteries. However, they have significant disadvantages requires constant improvements in this art.

One of the major drawbacks of the lead acid battery in which the electrolyte is sulfuric acid, is sulfation of electrode plates, reducing the capacity of the battery and reduce battery life. The best way to eliminate sulfate crystallization plates is the introduction of electrolyte additives that improve the performance of lead acid batteries.

As desulfatohirudin additives introduced into the sulfuric acid electrolyte, are used, for example, metal salts such as zinc sulfate, cadmium sulfate, or their mixture with salts of other metals, in particular transition metal sulfates, mercury [FR A1 2572854, H 01 M 10/36, 1986]. However, as known from practice, and from early publications [EN 2193808 C1, H 01 M 10/08, 2002] these additives do not regulate effectively the process e is Alisa, namely, does not reduce the self-discharge and gassing, which is a necessary condition for the optimal operation of the batteries, especially in confined areas. Known and other additives to the sulfuric acid electrolyte, which include: organic compounds, for example, dicarboxylic or tricarboxylic acid [JP, And 5272428, 1979], ethylcarboxylate Germany sesquioxide [JP A 59194367, 1984], amino acids [EP B1 0669670, H 01 M 10/08, 1999], nitrilotriethanol /NTF/ and hydroxyethylenediphosphonic /eddc/ acid [EN C1, 2115198, H 01 M 10/08, 1998]. In the electrolyte composition data of organic compounds often injected in a mixture with sulfates of the above metals. For example, the known electrolyte /EN 2115198/containing, in wt.%: cadmium sulfate 13-18, the sulfuric acid is 0.1-50, NTF 0,001-0,1, eddc 0,001-0,1, distilled water - the rest. The above acid /EN 2115198/ can also be introduced into the electrolyte as an additive, in which the content of the NTF is 0.001-0.1% by weight, HEDP acid of 0.001 to 0.15 wt.%. and the content of sulfate cadmium - 13-18% wt.

To extend the range of additives for lead acid batteries and create batteries with longer term actions proposed additive which is a mixture of sulfate of metal with phosphocarbonate acids and aminoalkylphosphonic or oxyalkylation acids diluted in the OI sulfuric acid environment, having a pH of not more than 0.8, and a total content of phosphonic acid, 0.001-0.015 percent wt., and sulfate of metal (in terms of metaln+) - 10-18 wt.%. The additive may further comprise a fluorine-containing surfactant in an amount of 0.01-0.1% by weight.

The main difference of the new composition from the composition of the prototype is to use as fosfororganicheskimi acid component of the mixture of three specific types of phosphonic acids, namely postantibiotic acids, aminoalkylphosphonic acids and oxyalkylation acids. As specific examples of phosphonic acids may be the following named representatives of the class:

- postantibiotic acid: licensecertificate of NOESN2N(CH2RHO3H2)2, bicarbonatesodachloride, (NOESN2)2HCH2RHO3H2, phosphonooxy HOOCCH2RHO3H2, phosphoproteome of NOESN2CH2RHO3H2;

- aminoalkylphosphonic acids: nitrilotriethanol N(CH2PO3H2)3, ethylenediaminetetramethylene [(H2About3RSN2)2NCH2]2, diethylenetriaminepentaacetate [(H2About3RSN2)2NCH2CH2]2NCH2PO3H2;

- oxyalkylation acids: oxoethylidene the background BUT(CH 3)With(RHO3H2)2.

These compounds, in a certain number of members additives in complex with sulfate of metal, provide high consumer properties of the batteries to which they are applied, namely the increase of the period of validity of batteries up to 5 years by preventing sulfate crystallization of the battery plates, and also by reducing self-discharge and outgassing when using batteries. This improves the environmental performance of batteries.

Used in the new composition of phosphonic acid, in all probability, have increased activity compared with the composition of the prototype due to the formation of complex mixed integrated systems not installed by the structure that most effectively participate in the process of desulfatation.

The essential feature of the composition is pH: not more than 0.8.

Included in the phosphonic acid is preferably introduced in a weight ratio of postantibiotic acids to aminoalkylphosphonic 1:1-1:3, or to oxyalkylation equal to 3:1, as can be seen from the following examples.

As the metal salt used sulphates of cadmium, zinc, tin. To make the frost resistance of the batteries in the composition of the new additives can be introduced and over OSTO-active fluorine-containing additive in an amount of 0.01-0.1% by weight. in relation to the weight of the whole mixture, which allows to use the battery filled with electrolyte with this additive at temperatures of up to -40°C.

To prevent sulfate crystallization of lead batteries new additive is introduced into the electrolyte in amounts as low as 0.01-0.03 in bulk amounts at 1 volumetric amount of electrolyte, after which the electrolyte is poured into the battery and is operated in the prescribed mode.

The following are specific examples of the additive composition further contains a description of technology of reception of the electrolyte with additives data and technology exploitation batteries with the electrolyte.

Composition 1. In the reactor, with a capacity of 50 DM3equipped with a mechanical stirrer and a dipstick, fill 33,5 DM3distilled water and stirring in portions at room temperature was added for 25-30 min 16.8 kg of cadmium sulfate, vosmiballnogo General formula CdSO4·8H2O. The suspension is stirred until the salt is completely dissolved cadmium for 1-1,5 hours. Then under stirring was added from a measuring device 29,4 cm3solution NTF obtained by dissolving 210 g NTF 4 DM3distilled water, and 29.4 cm3solution licensecertificate acid (GF)obtained by dissolving 276 g GF 4 DM3distillirovanna the th water. The ratio NTF: GF 1:1. The solution was adjusted to a pH of<0.8 add about 1.3 DM3electrolyte, representing a solution of sulfuric acid with a density of 1.27 g/cm3.

Thus obtained additive has a concentration of 0.075 g/DM3on PO43-that corresponds to a content of the mixture of phosphonic acids 0,0071% wt. and 14.3% Cd2+.

Part 2. Obtained from 15.5 kg cadmium sulfate, vosmiballnogo, 58,8 cm3solution NTF obtained by dissolving 210 g NTF 4 DM3distilled water, and 19,6 cm3solution fastnesses acid (FOOK)obtained by dissolving 293 g FOOK 4 DM3of distilled water. The ratio NTF: PHUC 3:1. After adding electrolyte to a pH of 0.7 additive has a concentration of 0.1 g/DM3on PO43-that corresponds to a content of the mixture of phosphonic acids 0,0084% wt., and 13.2% Cd2+.

Part 3. Obtained from 14,0 kg cadmium sulfate, vosmiballnogo, 73,5 cm3solution licensecertificate acid (GF)obtained by dissolving 276 g GF 4 DM3distilled water, and 24.5 cm3the HEDP solution obtained by dissolving 216 g eddc 4 DM3of distilled water. The ratio GF: eddc 3:1. After adding electrolyte to a pH of 0.7 additive has a concentration of 0.1 g/DM3on PO43-that is relevant to the duty to regulate the content of phosphonic acids 0,012% wt., and 11.8% Cd2+.

The proposed additive is used to prevent lead sulfate crystallization plates sulfuric acid batteries and to restore securitarian lead-acid batteries.

Example 1. The use of additives to prevent rechargeable batteries (to prevent sulfation). To 80 l of ready-to-electrolyte (sulfuric acid with a density of 1.27 g/cm3) add 1 l of additives (composition 1), stirred and poured into the battery, lead traction (AKB). After impregnation of the plates within 8-20 hours to produce charging the battery in the usual way.

Test the battery with electrolyte obtained in example 1, showed that the use of additives increases the inrush current and prevents the discharge. In result prevent sulfate crystallization plates AKB average lifespan is increasing.

Similar results were obtained with other compositions additives.

Example 2. Recovery of sulfated batteries. From the battery, the former in operation, merge the old electrolyte, washed plate 2-3 times with distilled water and pour the solution prepared by mixing 1 l of additives (composition 2) and 60 l of freshly prepared electrolyte (sulfuric acid with a density of 1.27 g/cm3). Spend 2-3 cycle charge-discharge depending on the extent of the su is hatachi plates. Thus for each cycle of the battery capacity increases by 15-30%. The battery capacity is restored to nominal after the next control discharge before the next charging it will be 70-80% of the nominal value.

Similar results were obtained with other compositions additives.

Example 3. The electrolyte prepared in accordance with example 1, add an additional surface-active compound based on performcalculation or performcalculation (fluorine surfactant) in the weighted number average of 0.015 wt.%. It was shown experimentally that the battery with the same electrolyte effectively operates at an ambient temperature up to 40°C.

Thus, prevention of sulfate crystallization battery plates by introducing into the electrolyte of the proposed additives increases the lifetime of efficient operation of lead-acid batteries and leads to improved performance properties.

1. Additive for sulfuric-acid lead acid batteries containing fosfororganicheskimi acid component and the metal sulfate in dilute sulfuric acid medium, characterized in that as fosfororganicheskimi acid component comprises a mixture of FotoCanvas acid oxyalkylation acid or aminoalkylphosphonic acid in the weight retained and the mixture of phosphonic acids, equal 0,004-0,015% wt., sulfate metal 10-18 wt.%. (in terms of metaln+) and the pH of the composition is not more than 0.8.

2. Additive according to claim 1, characterized in that it contains phosphocarbonate and aminoalkylphosphonic acid in a weight ratio of 1:1-1:3.

3. Additive according to claim 1, characterized in that it contains phosphocarbonate and oxyalkylation acid in a weight ratio of 3:1.

4. Additive according to claim 1, characterized in that it further contains a fluorine-containing surfactant in a weight amount as low as 0.01-0.1 wt.% relative to the total weight of the mixture.

5. The way to prevent sulfate crystallization of lead acid batteries by putting into the battery sulfuric-acid electrolyte containing an additive in amounts as low as 0.01-0.03 volume 1 volume of electrolyte, including fosfororganicheskimi component and a metal sulfate, where as fosfororganicheskimi component of the mixture is used FotoCanvas acid with oksietilidendifosfonovaya acid or aminoalkylphosphonic acid and subsequent operation of the battery.



 

Same patents:

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SUBSTANCE: electrolyte is doped with polyacrylamide in the amount of 0.001 to 6.0 mass percent per amount of electrolyte. Polyacrylamide added to electrolyte depends for its action on its coagulating properties and on increase of electrolyte viscosity which holds powdered active masses and products of reaction on electrolyte surface thereby preventing their fall-down, creeping, and wash-out. Polyacrylamide is introduced in the form of its aqueous solution before or after battery is filled with electrolyte to function as its additive.

EFFECT: improved operating characteristics and enhanced service life of batteries.

2 cl

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FIELD: chemical current supplies; electrolytes used for lead-acid batteries.

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2 cl

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5 cl, 3 ex

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1 cl, 1 tbl

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4 cl, 1 tbl

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11 cl, 5 ex

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23 cl, 9 tbl, 71 ex

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12 cl, 10 ex

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5 ex

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1 cl, 2 tbl, 5 ex

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