CN104143658B - Lead-acid storage battery and preparation method thereof - Google Patents

Abstract

The invention discloses a lead-acid storage battery and a preparation method thereof. The lead-acid storage battery comprises a positive plate and a negative plate. Coating of the negative plate of the lead-acid storage battery comprises, by weight, 1000 parts of lead powder, 1-20 parts of polyaspartic acid or poly-aspartate, 2-50 parts of silicon dioxide, 2-10 parts of barium sulfate, 4-20 parts of expanding agents, 80 parts of acid, 10 parts of mixed carbon and 106 parts of de-ionized water. By means of the lead-acid storage battery and the preparation method thereof, the battery failure due to the fact that the negative pole is sulfated is effectively delayed, negative pole hydrogen evolution caused by addition of a large amount of carbon is controlled, and the purposes that capacity of the lead-acid storage battery is improved, and the cycle life is prolonged are achieved. Moreover, carbon content of the negative pole of the storage battery is improved to a certain extent.

Description

A kind of lead-acid storage battery and preparation method thereof

technical field

The invention relates to a battery, in particular to a lead-acid battery and a preparation method thereof.

Background technique

The polar plates of lead-acid batteries are divided into positive and negative. In order to improve the performance of the positive and negative plates of lead-acid batteries, it is necessary to add positive and negative additives separately when manufacturing the positive and negative plates. Generally speaking, the additives for the positive plates are relatively simple, while The additives of the negative plate are more complex, including expansion agents, corrosion inhibitors and hydrogen evolution inhibitors. For example, commonly used expansion agents can be divided into inorganic expansion agents and organic expansion agents. Inorganic expansion agents include barium sulfate, carbon black, strontium sulfate, etc., which are conducive to the diffusion of electrolyte in the battery and the deep discharge of the battery; at the same time, it can effectively delay passivation. effect. Organic expansion agents include humic acid, lignin, lignin sulfonate, synthetic kneading materials, etc., which can prevent the specific surface area of the electrode from shrinking.

The addition of negative electrode additives can inhibit the solubility and solubility product of lead sulfate in the battery, and strengthen the discharge process of the negative electrode of the battery. However, various negative electrode additives have different effects on the discharge performance of the battery. The disadvantage of the crystal structure of lead sulfate during circulation is that it will be dissolved in the electrolyte, which will increase the polarization of the positive electrode and reduce the polarization of the negative electrode so that the sulfation of the negative electrode will diffuse. The conductivity of barium sulfate is worse than that of lead sulfate. It does not change when the potential of the negative electrode is exceeded. Barium sulfate enters the negative electrode and can be used as the nucleation center of lead sulfate, thus reducing the size of the formed lead sulfate crystals.

In addition, increasing the specific surface area is an effective method to increase the battery capacity and charge acceptance. Nakamura et al. proposed that adding carbon black to the negative electrode active material can effectively increase the specific surface area of the negative plate, and the chemical and electrochemical reactions on the negative plate not only occur on the surface of the lead phase but also on the surface of the carbon phase. Occurs on the surface, effectively improving the charge acceptance of the battery and delaying the accumulation of lead sulfate. However, if the carbon content in the plate is too much, it will cause a change in the potential of the negative electrode, and the hydrogen evolution potential will increase, resulting in serious hydrogen evolution, which will greatly reduce the cycle life of the battery.

With more and more research on lead-carbon batteries, how to control the hydrogen evolution at the negative electrode of the battery caused by the addition of a large amount of carbon, and delay the sulfation of the negative electrode to improve the cycle life of lead-acid batteries is an urgent problem.

The Chinese patent "Lead-Acid Battery Electrolyte and Preparation Method" with application number 201310668012.7 discloses a lead-acid battery electrolyte and a preparation method. ~2g, 1~2g sodium tetraborate, 0.1~0.5g stannous sulfate, 32~36g sulfuric acid and 58~65g pure water. The refinement of lead sulfate particles generated during the process, but because it is added to the electrolyte, sodium polyaspartate does not participate in the reaction process during the paste process, and the sulfuric acid generated during the paste process cannot be refined Lead particles, so it does not play a role in the conversion of lead sulfate into active substances during the chemical formation process. In addition, there is another disadvantage when adding it to the electrolyte, because sodium polyaspartate prevents or delays the formation of lead sulfate, which is not conducive to the discharge process, that is, the discharge capacity is low.

Contents of the invention

The purpose of the present invention is to overcome the deficiencies of the prior art and provide a lead-acid storage battery with large capacity and long service life and a preparation method thereof.

Above-mentioned purpose of the present invention is achieved by following technical scheme:

A kind of lead-acid accumulator, comprises positive pole plate and negative pole plate, and the coating of described lead-acid accumulator negative pole plate comprises each raw material component that following parts by weight form:

1000 parts of lead powder,

1~20 parts of polyaspartic acid or polyaspartic acid salt,

2~50 parts of silicon dioxide,

2~10 parts of barium sulfate,

4~20 parts of expansion agent,

80 parts of acid,

Mixed carbon 10 parts,

106 parts of water.

Preferably, the coating on the negative plate of the lead-acid storage battery includes each raw material component of the following parts by weight:

1000 parts of lead powder,

Polyaspartic acid or polyaspartate 10 parts,

26 parts of silicon dioxide,

6 parts of barium sulfate,

12 parts of expansion agent,

80 parts of acid,

Mixed carbon 10 parts,

106 parts of water.

Both polyaspartic acid and polyaspartic acid salt have good dispersing ability, and can disperse various particulate matter in aqueous solution, such as CaCO3, CaSO4, Ca3(PO4)2, etc., because the atomic radius of lead is the same as that of calcium , are all 180pp, so the addition of polyaspartic acid or polyaspartate can also effectively disperse lead sulfate crystals.

The introduction of polyaspartic acid or polyaspartic acid salt in the negative plate can promote the distortion of the crystal shape of PbSO4 crystals, which is due to the polyaspartic acid or polyaspartic acid salt and the Pb2+ in the formed PbSO4 small crystals The effect of physical adsorption and chemical adsorption occurs, so that an electric double layer is formed on the surface of the microcrystals, and there is an electrostatic repulsion between the microcrystals, which hinders the collision between them and the formation of large crystals. Polyaspartic acid or polyaspartate can form stable complexes with Pb2+ in aqueous solution, reduce the concentration of Pb2+ in aqueous solution, and reduce the possibility of forming PbSO4 precipitates. In addition, due to the good dispersion of polyaspartic acid or polyaspartate, the amount of carbon added to the negative plate can be increased.

Preferably, the polyaspartate is sodium polyaspartate or potassium polyaspartate.

The expansion agent is formed by mixing sodium lignosulfonate and humic acid in a mass ratio of 0.1-1:3. The mixed carbon graphite, acetylene black, activated carbon, and artificial carbon are mixed in a mass ratio of 4:3:2:1 or 3:3:2:2 or 4:4:1:1.

The acid is dilute sulfuric acid with a density of 1.4 g·mL-1.

Further, a method for preparing a lead-acid storage battery, comprising the steps of:

S1. Preparation of negative plate coating: mix lead powder, polyaspartic acid or polyaspartic acid salt, silicon dioxide, barium sulfate, expansion agent, and mixed carbon according to the stated ratio for 3 to 5 minutes, then add 106 parts Stir with water for 10 minutes, then add 80 parts of dilute sulfuric acid or dilute hydrochloric acid with a density of 1.4g·mL-1 while stirring. The acid addition time is controlled at 10-12 minutes. After the acid addition is completed, continue to stir for 10-15 minutes and control the temperature of the paste. at 60°C;

S2. Preparation of the negative electrode plate: coating the plate, soaking in acid, drying the surface, and then curing at 63°C and a relative humidity of 92% for no less than 48 hours, and then drying for 36 hours to form the negative electrode plate;

S3. Assemble the pole plates into the battery box, forming: put the polar plates into the welding tool to assemble the pole plate group, and then put the cast-welded or hand-welded pole plate group into the clean battery tank, positive and negative The poles are connected to each other, and then the plate group is assembled into a plate group, and finally formed;

S4. Injecting electrolyte: injecting electrolyte for formation, the perfusion volume is 8-15 mL per ampere hour, the electrolyte is a sulfuric acid solution, and the density of the sulfuric acid solution is 1.15-1.28 g/cm ³ .

Further, in the step S1, measure the apparent density of the paint 5 minutes before the paste is released. If it is too high, add an appropriate amount of water to adjust it. If it is lower than the specified value, appropriately prolong the stirring time until the apparent density is 4.25-4.35 g/cm ³ .

Compared with the prior art, the beneficial effects of the present invention are as follows:

(1) Adding polyaspartic acid (salt) to the coating of the negative electrode plate of the lead-acid battery is beneficial to control the shape and size of the lead sulfate crystals during the discharge process of the battery, form uniform lead sulfate crystal nuclei, and slow down the negative electrode sulfate. change.

(2) Adding polyaspartic acid (sodium) to the coating of the negative plate of the lead-acid battery can form a stable complex with Pb2+ in the electrolyte aqueous solution after the acid injection process is completed, reducing the Pb2+ concentration in the aqueous solution, Reduce the possibility of forming PbSO4 precipitates.

(3) The good dispersion of polyaspartic acid (salt) can also increase the amount of carbon added to the negative plate, increase the electrochemically active surface of the negative plate, reduce the self-discharge of the plate, and improve the charge and discharge of the lead-acid battery capacity and prolong the cycle life of the battery.

detailed description

The present invention will be further elaborated below through specific examples, but the examples do not limit the present invention in any form.

Example 1

A kind of lead-acid accumulator, comprises positive pole plate and negative pole plate, and the coating of described lead-acid accumulator negative pole plate comprises each raw material component that following parts by weight form:

1000 parts of lead powder,

1 part polyaspartic acid,

26 parts of silicon dioxide,

6 parts of barium sulfate,

12 parts of expansion agent,

80 parts of acid,

Mixed carbon 10 parts,

106 parts of water.

Further, the expansion agent is formed by mixing sodium lignosulfonate and humic acid in a mass ratio of 1:3; the mixed carbon is graphite, acetylene black, activated carbon, and artificial carbon in a mass ratio of 4:3:2 :1 by mixing; the acid is dilute sulfuric acid with a density of 1.4g·mL-1.

A preparation method for lead-acid storage battery, is characterized in that, comprises the steps:

S1. Preparation of negative plate coating: mix lead powder, polyaspartic acid, silicon dioxide, barium sulfate, expansion agent, and mixed carbon according to the stated ratio for 4 minutes, then add 106 parts of water and stir for 10 minutes, then add 80 parts Stir with dilute sulfuric acid or dilute hydrochloric acid with a density of 1.4g·mL-1, control the acid addition time at 11 minutes, continue to stir for 12 minutes after adding acid, and control the temperature of the paste to not exceed 60°C, the paste is produced, and the coating is measured 5 minutes before the paste is produced If the density is too high, add an appropriate amount of water to adjust it, if it is lower than the specified value, prolong the stirring time until the apparent density is 4.25-4.35g/cm ³ .

S2. Preparation of the negative electrode plate: coating the plate, soaking in acid, drying the surface, and then curing at 63°C and a relative humidity of 92% for no less than 48 hours, and then drying for 36 hours to form the negative electrode plate;

S3. Assemble the pole plates into the battery box, forming: put the polar plates into the welding tool to assemble the pole plate group, and then put the cast-welded or hand-welded pole plate group into the clean battery tank, positive and negative The poles are connected to each other, and then the plate group is assembled into a plate group, and finally formed;

S4. Injection of electrolyte solution: injection of electrolyte solution for formation, the perfusion volume is 11 mL per ampere hour, the electrolyte solution is a sulfuric acid solution, and the density of the sulfuric acid solution is 1.24 g/cm ³ .

Example 2

Except that polyaspartic acid is 10 parts in the coating of described lead-acid battery negative plate, other conditions are with embodiment 1;

Example 3

Except that polyaspartic acid is 20 parts in the coating of described lead-acid battery negative plate, other conditions are with embodiment 1;

Example 4

Except replacing polyaspartic acid with polyaspartic acid sodium, other conditions are with embodiment 1;

Example 5

Except that the sodium polyaspartate is 10 parts in the coating of described lead-acid accumulator negative plate, other conditions are with embodiment 2;

Example 6

Except that the sodium polyaspartate is 20 parts in the coating of described lead-acid accumulator negative plate, other conditions are with embodiment 2;

Comparative example 1

Except that described lead-acid accumulator negative plate does not add polyaspartic acid or sodium polyaspartate, other conditions are the same as embodiment 1;

Comparative example 2

Except that polyaspartic acid is 25 parts in the coating of described lead-acid battery negative plate, other conditions are with embodiment 1;

Comparative example 3

Except that the sodium polyaspartate is 25 parts in the coating of described lead-acid accumulator negative plate, other conditions are with embodiment 2;

Comparative example 4

Except that mixed carbon is 3 parts in the coating of described lead-acid storage battery negative plate, other conditions are with embodiment 2;

The lead-acid batteries prepared in Examples 1 to 6 and Comparative Examples 1 to 3 were tested for performance, and the results are shown in Table 1:

project First discharge capacity (Ah) cycle life Negative electrode carbon content Example 1 13.056 4015 1% Example 2 13.956 4435 1% Example 3 13.574 4227 1% Example 4 13.054 4018 1% Example 5 13.987 4440 1% Example 6 13.576 4229 1% Comparative example 1 10.368 3339 1% Comparative example 2 12.986 3987 1% Comparative example 3 12.865 3945 1% Comparative example 4 12.956 3986 0.3%

Comparative example 1 does not add polyaspartic acid (sodium), its initial discharge capacity and service life are all less than embodiment 1, 4, it can be seen that adding polyaspartic acid (sodium) can improve the charge and discharge capacity of lead-acid battery, prolong the battery life. cyclic service life; comparative example 2 discharge capacity and service life for the first time are all less than embodiment 1,2,3, it can be seen that the value range of polyaspartic acid in the coating of the present invention is optimal; comparative example 3 discharge capacity and service life for the first time All less than Example 4,5,6, it can be seen that the value range of sodium polyaspartate in the coating is optimal; the amount of mixed carbon in comparative example 4 is smaller than that of comparative example 1, but polyaspartic acid has been added acid, the initial discharge capacity and service life of Comparative Example 4 are greater than that of Comparative Example 1, combined with Example 2, it shows that polyaspartic acid is conducive to the increase of carbon content.

Claims (3)

1. a lead-acid storage battery, is characterized in that, the coating of described lead-acid storage battery negative plate comprises each raw material component that following weight part forms: 1000 parts of lead powder, Polyaspartic acid or polyaspartate 10 parts, 26 parts of silicon dioxide, 6 parts of barium sulfate, 12 parts of expansion agent, 80 parts of acid, Mixed carbon 10 parts, 106 parts of water; The swelling agent is formed by mixing sodium lignosulfonate and humic acid in a mass ratio of 0.1 to 1:3; The mixed carbon is formed by mixing graphite, acetylene black, activated carbon, and artificial carbon in a mass ratio of 4:3:2:1 or 3:3:2:2 or 4:4:1:1; Described acid is the dilute sulfuric acid of density 1.4g·mL ^-1 ; The polyaspartate is sodium polyaspartate or potassium polyaspartate. 2. a preparation method for the described lead-acid storage battery of claim 1, is characterized in that, comprises the steps: S1. prepare negative plate coating: lead powder, polyaspartic acid or polyaspartic acid salt, silicon dioxide, barium sulfate, expansion agent, mixed carbon are mixed and stirred by the raw material weight part described in claim 1 3 ~ After 5 minutes, add 106 parts of water and stir for 10 minutes, then add 80 parts of dilute sulfuric acid with a density of 1.4g·mL ^-1 while stirring. The acid addition time is controlled at 10-12 minutes. After the acid addition, continue to stir for 10-15 minutes and control the temperature of the kneading paste Not higher than 60 ℃, the paste; S2. Preparation of the negative plate: coating the plate, rinsing with acid, drying the surface, curing at 63°C and a relative humidity of 92% for no less than 48 hours, and then drying for 36 hours to form the negative plate; S3. Assemble the pole plates into the battery box, forming: put the polar plates into the welding tool to assemble the pole plate group, and then put the cast-welded or hand-welded pole plate group into the clean battery tank, positive and negative The poles are connected to each other, and then the plate group is assembled into a plate group, and finally formed; S4. Injecting electrolyte: injecting electrolyte for formation, the perfusion volume is 8-15 mL per ampere hour, the electrolyte is a sulfuric acid solution, and the density of the sulfuric acid solution is 1.15-1.28 g/cm ³ . 3. according to the preparation method of the described lead-acid storage battery of claim 2, it is characterized in that, 5 minutes before the pasting in described step S1 measures the apparent density of coating, if higher, add appropriate amount of water to adjust, if lower than the regulation, prolong appropriately Stir until the apparent density is 4.25-4.35g/cm ³ .