阅读说明：本技术 一种铅蓄电池负极板的制备方法 (Preparation method of negative plate of lead storage battery ) 是由 汤序锋 杨新明 张利棒 史凌俊 陈贤海 邱华良 杨慧琴 张腾 黄波 朱建峰 于 2021-08-25 设计创作，主要内容包括：本发明公开了一种铅蓄电池负极板的制备方法,在极板涂板后,先淋水再淋酸再将淋水和淋酸两部分产生的铅泥分别处理后回收利用。本发明通过对负极板淋水铅泥和淋酸铅泥回收再利用,能够解决负极铅膏的浪费问题,同时提高清洁化生产,降耗减排；本发明中的制作方法能够增加负极板栅表面的氧化层深度,增强负极铅膏与负极板栅的结合性,防止负极铅膏从板栅上脱落；增强铅蓄电池的充电接受能力、放电效率和循环寿命。(The invention discloses a preparation method of a negative plate of a lead storage battery. According to the invention, the negative plate water-spraying lead slime and acid-spraying lead slime are recycled, so that the waste problem of negative lead plaster can be solved, clean production is improved, consumption is reduced, and emission is reduced; the manufacturing method can increase the depth of the oxide layer on the surface of the negative plate grid, enhance the binding property of the negative lead plaster and the negative plate grid and prevent the negative lead plaster from falling off the plate grid; the charge acceptance, the discharge efficiency and the cycle life of the lead storage battery are enhanced.)

1. The preparation method of the negative plate of the lead storage battery is characterized by comprising the following steps:

(1) treating the negative plate after coating by a water spraying process to obtain a water sprayed negative plate and water sprayed lead mud;

(2) treating the negative plate after water spraying through an acid spraying process to obtain the negative plate after acid spraying and acid spraying lead mud;

(3) the treatment of the lead slime is carried out by water spraying,

dehydrating and drying the trickle lead mud, and grinding into powder to obtain trickle lead powder;

(4) the acid leaching lead mud is treated,

dehydrating and drying the acid leaching lead mud, and grinding into powder to obtain acid leaching lead powder;

(5) the manufacture of the regenerated negative plate is carried out,

the lead powder and the lead powder are mixed into recycled lead powder according to the mass of the lead powder not more than 20 percent of the lead powder,

when the negative plate is prepared into paste, the recovered lead powder is added in a proportion of not more than 5% of the total mass of the lead powder.

2. The method of claim 1, wherein the speed of coating the sheet in step (1) is 120 negative plates per minute.

3. The preparation method according to claim 1, wherein the lead powder for showering and the lead powder for showering in the step (5) are mixed into the recovered lead powder according to the condition that the lead powder for showering accounts for 20% of the mass of the lead powder for showering,

when the negative plate is prepared into paste, the recovered lead powder is added in a proportion of 5% of the mass of the lead powder.

4. The method of claim 1, wherein in step (4), the dried lead acid powder is ground and sieved through a 100 mesh sieve.

5. The method according to claim 1, wherein in the step (4), the iron content of the dried leached lead powder is less than or equal to 0.0005% by mass.

6. The preparation method according to claim 1, wherein in the step (5), the components in the formula comprise, by mass percent of the total lead powder, 0.3% of acetylene black, 0.05% of sodium lignosulfonate, 0.5% of humic acid, 0.08% of short cellulose, 0.6% of sodium sulfate, 11% of pure water and 1.40g/cm of density³8.5% sulfuric acid solution.

7. The manufacturing method according to claim 1, wherein the processes in steps (1) and (2) are performed by using a regenerated negative plate manufacturing apparatus, the regenerated negative plate manufacturing apparatus comprises a conveying mechanism for conveying the negative plates after plate coating, the conveying mechanism comprises a water spraying station and an acid spraying station which are distributed along a conveying direction, a water spraying lead mud collecting tank for collecting water spraying to generate water spraying lead mud is arranged below the water spraying station, and a acid spraying lead mud collecting tank for collecting acid spraying to generate acid spraying lead mud is arranged below the acid spraying station.

8. A negative plate for a lead-acid battery produced by the production method according to any one of claims 1 to 7.

9. A lead-acid storage battery comprising a negative plate, wherein the negative plate is the negative plate for a lead-acid storage battery according to claim 8.

Technical Field

The invention belongs to the technical field of lead storage batteries, and particularly relates to a preparation method of a negative plate of a lead storage battery.

Background

In the production and manufacturing process of the polar plate of the lead storage battery, the plate coating is a process of coating lead plaster on a grid. In order to ensure the quality of a final finished product and prevent excessive water loss on the surface of the polar plate, the surface of the wet polar plate is subjected to acid spraying treatment after the plate is coated, a sulfuric acid layer is formed on the surface of the polar plate subjected to the acid spraying treatment, and the formed sulfuric acid layer can effectively prevent the surface of the polar plate from cracking. Lead slime for acid leaching can be generated in the acid leaching process of the polar plate, and particularly, the yield of the generated acid leaching lead slime is high when two acid leaching processes are adopted by most polar plate manufacturers, and even more than 2% of the acid leaching lead slime is generated.

At present, the traditional treatment modes of acid leaching lead slime include the following steps:

1. is directly scrapped

At present, most manufacturers can directly scrap the acid leaching lead slime, the cost difference is about 5000 yuan/ton, the acid leaching lead slime belongs to dangerous waste and solid, a large amount of lead powder is contained in the lead slime, and the direct waste treatment of the acid leaching lead slime can not only cause serious environmental problems, but also cause great waste of resources.

2. Drying, grinding into powder, directly adding, recycling and utilizing

Patent document (CN 106129515a) discloses a method for recycling and utilizing solid waste acid leaching lead mud of a storage battery electrode plate, which is to collect lead-containing suspension acid liquor, immediately separate lead powder in the lead-containing suspension acid liquor from the acid leaching acid liquor by a filter pressing method, collect, dry, crush and remove impurities from the recovered lead powder, and then recycle the lead powder according to the components and the quantity of the lead powder.

Patent document (CN 103647116a) discloses a lead slime recycling method, which includes the following steps: (1) recovering lead slime: the lead slime separated by the filter press is filled into a charging barrel; (2) and (3) drying: putting the charging barrel filled with the lead slime into a curing chamber for drying to ensure that the water content of the lead slime in the charging barrel is less than 3 percent; (3) polishing and sieving: polishing the solidified lead slime through a grinding machine, and then sieving the lead slime through an 80-mesh sieve; (4) and (3) recovering: and (4) conveying the ground lead powder to a paste mixer again for recycling.

Patent document (CN 110400908B) discloses a method for recycling waste lead plaster in a storage battery plate coating process, which comprises the following steps: (1) collecting waste lead plaster generated in the plate coating process; (2) washing the waste lead plaster with water to remove redundant additives in the waste lead plaster; (3) removing redundant acid water in the waste lead plaster to obtain wet lead plaster; (4) uniformly stirring the wet lead slime, and then putting the wet lead slime into a curing chamber for curing and drying; (5) after the solidification and drying are finished, crushing the lead slime to obtain lead slime powder; (6) adding the lead slime powder into the lead plaster for use.

Because the acid leaching lead mud basically mainly comprises lead sulfate, about 60-80 percent, and 10-20 percent of lead oxide, if the dried acid leaching lead powder is directly added, the dried acid leaching lead powder is difficult to be converted into an active substance, the weight of the polar plate is only increased, the capacity of the polar plate is not increased, no significance is realized, and the capacity of the lead storage battery is influenced.

Therefore, the acid leaching lead slime is reasonably used, direct economic loss can be reduced, and great profit margin exists. How to recycle and convert the leached lead mud into effective active substances is a technical problem faced by those skilled in the art.

Disclosure of Invention

The invention discloses a preparation method of a negative plate of a lead storage battery, and aims to solve the problems of resource waste and environmental pollution caused by the loss of lead slime in the manufacturing process of the negative plate of the lead storage battery.

A preparation method of a negative plate of a lead storage battery comprises the following steps:

(1) treating the negative plate after coating by a water spraying process to obtain a water sprayed negative plate and water sprayed lead mud;

(2) treating the negative plate after water spraying through an acid spraying process to obtain the negative plate after acid spraying and acid spraying lead mud;

(3) the treatment of the lead slime is carried out by water spraying,

dehydrating and drying the trickle lead mud, and grinding into powder to obtain trickle lead powder;

(4) the acid leaching lead mud is treated,

dehydrating and drying the acid leaching lead mud, and grinding into powder to obtain acid leaching lead powder;

(5) the manufacture of the regenerated negative plate is carried out,

the lead powder and the lead powder are mixed into recycled lead powder according to the mass of the lead powder not more than 20 percent of the lead powder,

when the negative plate is prepared into paste, the recovered lead powder is added in a proportion of not more than 5% of the total mass of the lead powder. Wherein, the total lead powder is the sum of the recovered lead powder and the normal newly produced lead powder.

The water and acid spraying are performed synchronously with the plate coating process, so that the water and acid spraying speed is consistent with the plate coating speed. Preferably, the speed of coating the plate in the step (1) is 120 negative plates per minute. Washing the redundant lead slime and residual paste on the surface of the negative plate by a first stage of water spraying process at the speed of 120 smears within 1 minute, wherein the lead slime is mainly PbO lead paste and does not contain PbSO₄The components of the finally prepared lead plaster for water spraying are consistent with those of lead plaster during plate coating, so that the lead plaster is added into the lead plaster during reuse, and the performance of the polar plate is not influenced; after water spraying, the second stage of acid spraying process is carried out again, and the acid spraying process reacts with the surface of the active substance of the negative plate to form a layer of PbSO₄Protective layer, in which case PbSO is generated₄The lead plaster produced by the acid leaching has changed components due to the reaction with sulfuric acid, so the lead plaster cannot be added in a large amount for recycling, and the performance of the polar plate is influenced otherwise.

Preferably, the lead powder for water spraying and the lead powder for acid spraying in the step (5) are mixed into recycled lead powder according to the condition that the lead powder for acid spraying accounts for 20% of the mass of the lead powder for water spraying; when the negative plate is prepared into paste, the recovered lead powder is added in a proportion of 5% of the mass of the lead powder.

Preferably, in the step (4), the dried acid leaching lead powder is crushed and sieved by a 100-mesh sieve. After the lead paste is sieved by a 100-mesh sieve, the recycled acid-leaching lead powder particles are fine and uniform, impurities such as sand are prevented from being contained, subsequent paste mixing is more uniform, and the lead paste binding performance is stronger

Preferably, in the step (4), the iron content of the dried acid leaching lead powder is less than or equal to 0.0005% by mass.

Preferably, in the step (5), the components in the formula comprise, by mass percent, 0.3% of acetylene black, 0.05% of sodium lignosulfonate, 0.5% of humic acid, 0.08% of short cellulose, 0.6% of sodium sulfate, 11% of pure water and 1.40g/cm of density³8.5% sulfuric acid solution.

Preferably, the preparation method uses a regenerated negative plate preparation device to perform the treatment of the steps (1) and (2), the regenerated negative plate preparation device comprises a conveying mechanism for conveying the negative plates after the plates are coated, the conveying mechanism is provided with a water spraying station and an acid spraying station which are distributed along the conveying direction, a water spraying lead mud collecting tank for collecting water spraying and producing water spraying lead mud is arranged below the water spraying station, and an acid spraying lead mud collecting tank for collecting acid spraying and producing acid spraying lead mud is arranged below the acid spraying station.

The invention also provides the negative plate of the lead storage battery prepared by the preparation method.

The invention also provides a lead storage battery, which comprises the negative plate, wherein the negative plate is the negative plate of the lead storage battery.

Compared with the prior art, the invention has the following advantages:

according to the invention, the negative plate water-spraying lead slime and acid-spraying lead slime are recycled, so that the waste problem of negative lead plaster can be solved, clean production is improved, consumption is reduced, and emission is reduced; the manufacturing method can increase the depth of the oxide layer on the surface of the negative plate grid, enhance the binding property of the negative lead plaster and the negative plate grid and prevent the negative lead plaster from falling off the plate grid; the charge acceptance, the discharge efficiency and the cycle life of the lead storage battery are enhanced.

Drawings

FIG. 1 is a schematic diagram of a process and an apparatus for preparing a negative plate of a lead-acid battery.

Fig. 2 shows the cycle life test results, wherein a: comparative example 1; b: example 1.

Detailed Description

The preparation method of the negative plate of the application is as follows: the treatment of the coating plate of the negative plate and the drenching and acid drenching after the coating plate is carried out by using the regeneration negative plate preparation device shown in figure 1, the regeneration negative plate preparation device comprises a conveying mechanism for conveying the negative plate after the coating plate, the conveying mechanism is provided with a drenching station and an acid drenching station which are distributed along the conveying direction, a drenching lead mud collecting tank for collecting drenching lead mud is arranged below the drenching station, and a drenching acid lead mud collecting tank for collecting drenching acid and producing drenching acid lead mud is arranged below the acid drenching station. The coating speed was 120 negative plates per minute. Treating the negative plate after coating by a water spraying process to obtain a water-sprayed negative plate and water-sprayed lead mud, dehydrating and drying the water-sprayed lead mud, and grinding the water-sprayed lead mud into powder to obtain water-sprayed lead powder; and (3) treating the negative plate subjected to water spraying through an acid spraying process to obtain the negative plate subjected to acid spraying and acid spraying lead mud, dehydrating and drying the acid spraying lead mud, and grinding the acid spraying lead mud into powder to obtain acid spraying lead powder. And mixing the trickle lead powder and the acid leaching lead powder in proportion to obtain recovered lead powder, and adding the recovered lead powder in proportion for use when the negative plate is used for preparing a paste mixture.

Example 1

Filtering sandy soil impurities of the drenching lead slime by using gauze to obtain drenching lead slime with the impurities removed; and dehydrating and drying the impurity-removed lead slime, and then grinding to obtain dried impurity-removed lead powder.

And squeezing and dehydrating acid leaching lead paste generated in the acid leaching process, drying at 80 ℃ for 12h, grinding into powder, and sieving with a 100-mesh sieve to ensure that the mass content of iron is less than or equal to 0.0005 percent to obtain the dried acid leaching lead powder.

The two kinds of recovered lead slime, namely the water-drenching lead slime and the acid-drenching lead slime, are respectively tested according to the standards in the table 1, and are recycled after reaching the specified specific gravity and moisture content of the lead plaster.

TABLE 1 technical index of lead powder recovery

Sampling detection is carried out on the recovered lead powder according to the technical indexes in the table 1, and the test results are shown in the table 2.

Table 2 moisture and specific gravity testing of mixed pastels

And mixing acid mud generated in the water spraying process and lead mud generated in the acid spraying process according to the mass ratio of 5: 1 to obtain recovered lead powder.

The recovered lead powder is added in a proportion of 5% of the total lead powder mass. The added formula materials are calculated according to the mass percentage of lead powder: 0.3% of acetylene black, 0.05% of sodium lignosulfonate, 0.5% of humic acid, 0.08% of short cellulose, 0.6% of sodium sulfate, 11% of pure water, 8.5% of sulfuric acid and 1.40g/cm of sulfuric acid density³(25 ℃ C.). Stirring to obtain regenerated negative lead plaster; and coating the regenerated negative lead plaster to obtain the regenerated negative plate.

And assembling the regenerated negative plate and the conventional positive plate to obtain the lead storage battery.

Example 2

Filtering sandy soil impurities of the drenching lead slime by using gauze to obtain drenching lead slime with the impurities removed; dehydrating and drying the impurity-removed lead slime, and then grinding to obtain dried impurity-removed lead powder;

squeezing and dehydrating acid leaching lead plaster generated in the acid leaching process, drying at 80 ℃ for 12h, grinding into powder, and sieving with a 100-mesh sieve to ensure that the iron content is less than or equal to 0.0005 percent to obtain dry acid leaching lead powder;

the two kinds of recovered lead slime, namely the water-drenching lead slime and the acid-drenching lead slime, are respectively tested according to the standards in the table 1, and are recycled after reaching the specified specific gravity and moisture content of the lead plaster.

The mixed lead paste was sampled and tested according to the moisture and specific gravity standards in table 1. The test results are shown in table 3.

Table 3 moisture and specific gravity testing of mixed pastels

And mixing acid mud generated in the water spraying process and lead mud generated in the acid spraying process according to the mass ratio of 5: 1 to obtain recovered lead powder.

The recovered lead powder is added in a proportion of 5% of the total lead powder mass. The formula materials comprise, by mass, 0.3% of acetylene black, 0.05% of sodium lignosulphonate, 0.5% of humic acid, 0.08% of short fiber, 0.6% of sodium sulfate, 11% of pure water, 8.5% of sulfuric acid and 1.40g/cm of sulfuric acid density³(25 ℃) to obtain regenerated negative lead paste; and coating the regenerated negative lead plaster to obtain the regenerated negative plate.

And assembling the regenerated negative plate and the conventional positive plate to obtain the lead storage battery.

Comparative example 1

The process of only leaching acid and recycling the recovered lead plaster in the prior art is adopted, and compared with the process of recycling the lead plaster by leaching water and leaching acid, the amount of the recovered lead plaster is shown in the table 4.

TABLE 4 comparison of recovered lead paste amounts

Negative plates and lead storage batteries were prepared by the same method as in example 1 using acid-showering lead paste recovered by the prior art only acid-showering process for comparison.

Example 3

The negative electrode plates and the finished lead-acid batteries prepared in examples 1 and 2 were sampled and inspected.

1. And sampling and detecting the negative plate, detecting the separation condition of the negative plate grid and the active substances, and verifying the bonding strength of the negative plate grid and the active substances. The positive and negative electrode plates were respectively faced down and subjected to 3 drop tests from a height of 1 m each. And when the loss amount of the negative pole lead paste is less than or equal to 1.0%, judging the negative pole plate to be qualified, wherein the smaller the percentage value is, the thicker the oxidation layer is, the stronger the associativity is, the less the lead paste is lost by falling, and the thinner the oxidation layer is. The test results are shown in table 5.

TABLE 5 plate drop confirmation grid and active material binding test

2. And sampling and detecting the negative plate of the finished lead storage battery, and testing the specific surface area, the pore volume and the average pore diameter of the negative plate lead paste. When the specific surface area is more than or equal to 0.60m²And when the specific surface area is/g, judging that the specific surface area of the negative plate lead paste meets the standard requirement. The test results are shown in table 6. The normal lead paste in the table means that the recovered lead powder is not added, and the other preparation methods are the same as those in examples 1 and 2.

TABLE 6 pore volume, mean pore diameter and specific surface area of the pastes

Type (B)	Specific surface area m2/g	Pore volume cm3/g	Average pore diameter nm
				Normal lead plaster	0.4842	0.001577	13.0298
Example 1	0.6163	0.003326	20.0984
				Example 2	0.6281	0.003326	20.0984

As can be seen from table 6, the specific surface area, pore volume, and average pore diameter of the negative electrode lead paste prepared by adding 20% of the recovered lead powder were increased.

3. And sampling and detecting the dry lead plaster of the negative plate, and testing the impurity content of the dry lead plaster Fe of the negative plate. When the impurity content of Fe is less than or equal to 0.0005 percent, the lead plaster is qualified and meets the requirement. The test results are shown in table 7.

TABLE 7 impurity content (% by mass) of dry lead paste of negative plate

	Ag	Zn	Fe	Cu	Mg	Sb
							Normal lead plaster	0.00012	0.00009	0.00003	0.00030	0.00009	＜0.0001
Example 1	0.00011	0.00012	0.00020	0.00029	0.00012	＜0.0001
							Example 2	0.00010	0.00010	0.00031	0.00028	0.00011	＜0.0001

When lead paste is recycled, the requirement on the content of iron element is mainly met, and the influence of the iron element on the performance is large, so that the active substances of the pole plate are early argillized and fall off, and the self-discharge is fast. As can be seen from table 7, the impurity content of Fe in the dry lead paste of the negative plate to which 20% of the recovered lead powder was added was still within the acceptable range and could be used.

4. The capacity of the assembled lead storage battery is sampled and detected, and the capacity is judged according to the standard (GB _ T22199.2-2017 national standard). The test results are shown in table 8.

Table 8C 20, 3C, 5C performance tests of assembled lead acid batteries

	C20	3C	5C
				Standard of merit	Not less than 20 hours	Greater than 8 hours	Greater than 3 hours
Normal lead plaster	22 hours 45 minutes	9 hours and 48 minutes	3 hours and 42 minutes
				Example 1	22 hours and 40 minutes	9 hours and 36 minutes	3 hours and 26 minutes
Example 2	22 hours and 38 minutes	9 hours 33 minutes	3 hours and 28 minutes

Table 8 the performance was tested on 12V20Ah size cells with C20 being a 20 hour rate discharge method using a discharge time from constant current 10A discharge to the end of 10.5V final voltage. 3C is the discharge time from the end voltage of 10.5V with a discharge rate of 3 times 10A. 5C is the discharge time from 5 times of 10A discharge rate to 10.5V end voltage. As can be seen from Table 8, the addition of 20% of the recycled lead powder has no significant effect on the capacity of the lead-acid battery, and the capacity still meets the standard requirements.

5. Self-discharge condition

When 1 cell (12V20Ah standard) of comparative example 1 and example 1 was sampled and left to stand at ambient temperature of 25 ℃ for 1 week, 2 weeks, 3 weeks and 4 weeks, and the open circuit voltage of each cell was recorded, the voltage value showed that the voltage drop rate of the cell of example 1 was slower than that of the cell of comparative example 1, indicating that the self-discharge performance was good, and the results are shown in Table 9.

TABLE 9 self-discharge test results

	1 week	2 weeks	3 weeks	4 weeks	Reduced voltage
						Comparative example 1	13.25V	13.23V	13.21V	13.19V	0.06V
Example 1	13.25V	13.24V	13.23V	13.22V	0.03V

6. Cycle life detection of finished lead storage batteries

The batteries of example 1 and comparative example 1 were sampled for 1 group (12V20Ah specification, 4 batteries in series) and subjected to cycle life test, and a charging current of 8A, a charging limit voltage of 59.2V and a charging time of 8 hours were set. Discharge 10A, end voltage 42V is one cycle period.

As shown in fig. 2, it can be seen from the performance test data that the battery of example 1 has a longer cycle life and a higher capacity than the battery of comparative example 1.