阅读说明：本技术 一种铅酸蓄电池用电解液及包含该电解液的铅酸蓄电池 (Electrolyte for lead-acid storage battery and lead-acid storage battery comprising electrolyte ) 是由 李焙 杨富麟 蒋岚 于 2020-11-04 设计创作，主要内容包括：本发明涉及一种解决电池化成过程中产生过多气泡的问题,既保护环境、设备及工作人员安全,又能降低化成过程中电解液的温度,提升电池性能的铅酸蓄电池用电解液及包含该电解液的铅酸蓄电池,包括胶体酸与二苯基(硅氧烷和聚硅氧烷)。本发明中,二苯基(硅氧烷和聚硅氧烷)性质稳定,不参与化成过程中的化学反应；而且解决了铅酸蓄电池化成过程中产生气泡过多的问题,即使电池在低温或者高温环境条件下使用,本发明的电解液均不会受影响；使用本发明的电解液,能使电池性能得到提升,并对环境、设备、人身安全起到了保护作用。(The invention relates to an electrolyte for a lead-acid storage battery and the lead-acid storage battery containing the electrolyte, which solve the problem of excessive bubbles generated in the formation process of the battery, protect the safety of the environment, equipment and workers, reduce the temperature of the electrolyte in the formation process and improve the performance of the battery, and comprises colloidal acid and diphenyl (siloxane and polysiloxane). In the invention, diphenyl (siloxane and polysiloxane) has stable property and does not participate in chemical reaction in the formation process; the problem of excessive bubbles generated in the formation process of the lead-acid storage battery is solved, and the electrolyte of the invention is not affected even if the battery is used under the low-temperature or high-temperature environment condition; the electrolyte can improve the performance of the battery and protect the environment, equipment and personal safety.)

1. An electrolyte for a lead-acid storage battery is characterized by comprising a colloidal acid and a siloxane material.

2. The electrolyte for lead-acid storage batteries according to claim 1, wherein said siloxane-based material is added in an amount of 0.01-0.8% by weight based on the weight of the colloidal acid.

3. The electrolyte for lead-acid storage batteries according to claim 1, wherein said siloxane-based material is added in an amount of 0.05-0.5% by weight based on the weight of the colloidal acid.

4. The electrolyte for lead-acid storage batteries according to claim 1, wherein said siloxane-based material is added in an amount of 0.1-0.3% by weight based on the weight of the colloidal acid.

5. The electrolyte for lead-acid storage batteries according to claim 1, 2, 3 or 4, wherein said siloxane-based material is diphenyl (siloxane and polysiloxane) and has a density of 1.1-1.3g/cm³。

6. The electrolyte for a lead-acid storage battery according to claim 1, wherein the preparation method of the colloidal acid comprises: adding deionized water into the gas phase silicon dioxide, stirring for 40-60min to obtain a colloid mother solution, and then adding dilute sulfuric acid and stirring to obtain the catalyst.

7. The electrolyte for lead-acid storage batteries according to claim 6, wherein the mass fraction of fumed silica in said colloidal mother liquor is 15%.

8. The electrolyte for lead-acid storage batteries according to claim 6, wherein the conductivity of said deionized water is less than or equal to 1.5 μ s/cm.

9. According to claim6 the electrolyte for the lead-acid storage battery is characterized in that the density of the dilute sulfuric acid is 1.262g/cm³The density of the colloidal acid is 1.250g/cm³。

10. A lead-acid storage battery comprising a positive electrode, a negative electrode, a separator and the electrolyte according to any one of claims 1 to 9.

Technical Field

The invention belongs to the field of storage batteries, relates to a storage battery electrolyte, and particularly relates to an electrolyte for a lead-acid storage battery and the lead-acid storage battery containing the electrolyte, which can solve the problem of excessive bubbles generated in the formation process of the battery, protect the safety of the environment, equipment and workers, reduce the temperature of the electrolyte in the formation process, and improve the performance of the battery.

Background

In recent years, with the development of the photovoltaic power generation industry and the wind power generation industry, a large-capacity storage battery is generally required by the market to be matched with energy storage, but the conventional storage battery has short service life and high waste rate in outdoor use, and the commercial application of a photovoltaic energy storage system is restricted. It is generally agreed in the industry that the service life of the lead storage battery in the open air can be effectively prolonged by adding a proper amount of colloidal substances into sulfuric acid solution of the lead storage battery.

The colloid material traditionally used in the lead storage battery industry is fumed silica, and the fumed silica is fully liquefied by industrial pure water or other solvent methods when in use; in the Chinese patent ZL01109623.3, a siloxane composition is disclosed, which is prepared by mixing poly-element siloxane, organic silicon rubber and water for dilution, and the composition is mixed with sulfuric acid solution and used as electrolyte or formation solution of lead storage battery. Through decades of applications, the industry generally considers that fumed silica colloid and siloxane composition colloid have thousands of years, the former has high viscosity and poor manufacturability, lead storage batteries have no benefit of reducing internal resistance and increasing capacity, but the service life attenuation is smooth, and the latter has low viscosity and good manufacturability, and lead storage batteries can obtain the benefit of reducing internal resistance and increasing capacity, but the stability is inferior to the former.

In the formation process of the lead-acid storage battery, water can be electrolyzed due to large-current charging to generate a plurality of bubbles, and the bubbles carry sulfuric acid, so that acid mist is easily formed, the environment is polluted, equipment such as a water forming tank, a protective guard, a charging wire and the like can be corroded, and the safety protection of workers is not facilitated; too much air bubbles can also cause the temperature of the electrolyte to rise, affecting the performance of the lead-acid battery.

Disclosure of Invention

The invention aims to solve the defects that bubbles are generated in the formation process of the conventional lead-acid storage battery, equipment is corroded, the environment is polluted, and the safety of workers is not facilitated, and provides the electrolyte for the lead-acid storage battery, which solves the problem that excessive bubbles are generated in the formation process of the battery, protects the safety of the environment, the equipment and the workers, reduces the temperature of the electrolyte in the formation process, and improves the performance of the battery.

It is another object of the present invention to provide a lead-acid battery comprising the electrolyte.

In order to achieve the purpose, the invention adopts the following technical scheme:

an electrolyte for a lead-acid battery, the electrolyte comprising a colloidal acid and a siloxane-based material.

Preferably, the siloxane-based material is added in an amount of 0.01 to 0.8% by weight of the colloidal acid.

Preferably, the siloxane-based material is added in an amount of 0.05 to 0.5% by weight of the colloidal acid.

Preferably, the siloxane-based material is added in an amount of 0.1 to 0.3% by weight of the colloidal acid.

Preferably, the siloxane-based material is diphenyl (siloxane and polysiloxane) and has a density of 1.1-1.3g/cm³。

In order to solve the problem of excessive bubbles generated in the formation process of the lead-acid storage battery and further improve the performance of the battery, the invention provides a storage battery electrolyte formula, wherein diphenyl (siloxane and polysiloxane) is added into the formula, and the CAS number: 63148-59-4.

The defoaming agent in the current market is mainly organic silicon, polyether and high carbon alcohol, and has the defects that: the defoaming speed of the polyether defoaming agent is relatively slow, and the high-carbon alcohol defoaming agent canBoth are not suitable to be used as the defoaming auxiliary agent in the formation process of the lead-acid storage battery when participating in the reaction. The silicone is mostly polydimethylsiloxane which has hydrophobicity, is nontoxic and has stable property, and the polydimethylsiloxane has small surface tension when being used for a long time at the temperature of between 50 ℃ below zero and 200 ℃ and can be diffused in the foam, a double-layer film is formed on the foam wall by diffusion elbow, and the surfactant with the stabilizing effect is discharged in the diffusion process, so that the surface tension of the foam is reduced, the self-healing effect of the foam is destroyed, and the foam is broken; the density of the polydimethylsiloxane fluid is less than 1.0g/cm³(25 ℃), and the electrolyte of the lead-acid storage battery has the lowest density state when discharging is still more than 1.0g/cm³(25 ℃), the maximum state of charge can reach 1.36g/cm³(25 ℃ C.), the polydimethylsiloxane acts only on the bubbles on the surface of the electrolyte, and defoams the surface, and cannot suppress the generation of bubbles in the electrolyte.

The diphenyl (siloxane and polysiloxane) has the following advantages over polydimethylsiloxane: 1) diphenyl (siloxane and polysiloxane) has polydimethylsiloxane and is also organosilicon, has similar physical and chemical properties and is influenced by symmetrical phenyl, and compared with polydimethylsiloxane, diphenyl (siloxane and polysiloxane) has lower freezing point, higher boiling point and more stable chemical properties and cannot be solidified or oxidized to fail due to the use of the lead-acid battery electrolyte under extreme conditions; 2) the density of the diphenyl (siloxane and polysiloxane) liquid was 1.2g/cm³At about 25 ℃, in the formation process, along with the change of the density of the electrolyte, diphenyl (siloxane and polysiloxane) continuously contacts with molecules in the electrolyte, so that the generation of bubbles is inhibited, the temperature of the electrolyte is better reduced, and the defoaming and foam inhibiting effects are achieved; 3) in addition, the density of the polyphenylmethylsiloxane is 1.09g/cm³About (25 ℃), the ability to suppress bubbles is inferior to diphenyl (siloxane and polysiloxane) and less stable than it is; and too high phenyl content, such as triphenyl, tetraphenyl, etc., has large liquid viscosity, stronger hydrophobicity, poor dispersibility in the electrolyte, and difficult defoaming effect. Therefore, the lead-acid storage battery formula has irreplaceable effectThe ability of the foam to suppress foam.

Preferably, the preparation method of the colloidal acid comprises the following steps: adding deionized water into the gas phase silicon dioxide, stirring for 40-60min to obtain a colloid mother solution, and then adding dilute sulfuric acid and stirring to obtain the catalyst.

Preferably, the mass fraction of fumed silica in the colloid mother liquor is 15%.

Preferably, the conductivity of the deionized water is less than or equal to 1.5 mu s/cm.

Preferably, the density of the dilute sulfuric acid is 1.260g/cm³The density of the colloidal acid is 1.250g/cm³。

A lead-acid storage battery comprises a positive electrode, a negative electrode, a separator and the electrolyte.

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

1) diphenyl (siloxane and polysiloxane) has polydimethylsiloxane and is also organosilicon, has similar physical and chemical properties and is influenced by symmetrical phenyl, and compared with polydimethylsiloxane, diphenyl (siloxane and polysiloxane) has lower freezing point, higher boiling point and more stable chemical properties and cannot be solidified or oxidized to fail due to the use of the lead-acid battery electrolyte under extreme conditions;

2) the density of the diphenyl (siloxane and polysiloxane) liquid was 1.2g/cm³At about 25 ℃, in the formation process, along with the change of the density of the electrolyte, diphenyl (siloxane and polysiloxane) continuously contacts with molecules in the electrolyte, so that the generation of bubbles is inhibited, the temperature of the electrolyte is better reduced, and the defoaming and foam inhibiting effects are achieved;

3) the density of the polyphenylmethylsiloxane is 1.09g/cm³About (25 ℃), the ability to suppress bubbles is inferior to diphenyl (siloxane and polysiloxane) and less stable than it is; and too high phenyl content, such as triphenyl, tetraphenyl, etc., has large liquid viscosity, stronger hydrophobicity, poor dispersibility in the electrolyte, and difficult defoaming effect. Therefore, the lead-acid storage battery formula has the irreplaceable defoaming and foam inhibiting capability;

4) diphenyl (siloxane and polysiloxane) is stable in property and does not participate in chemical reaction in a formation process; the problem of excessive bubbles generated in the formation process of the lead-acid storage battery is solved, and the electrolyte of the invention is not affected even if the battery is used under the low-temperature or high-temperature environment condition; the electrolyte can improve the performance of the battery and protect the environment, equipment and personal safety.

Drawings

FIG. 1 is a process flow diagram of the electrolyte of the present invention.

FIG. 2 is a graph showing the cycle test of examples 1-2 of the present invention and comparative examples 1-2.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Diphenyl (siloxane and polysiloxane) used in the present invention, CAS No.: 63148-59-4, the density of the diphenyl (siloxane and polysiloxane) liquid is 1.2g/cm³About 25 ℃ C, and is commercially available.

The rest raw materials used in the invention can be obtained from the market.

Example 1

This example provides an electrolyte for a lead-acid battery, which includes a colloidal acid and diphenyl groups (siloxane and polysiloxane), wherein the addition amount of the diphenyl groups (siloxane and polysiloxane) is 0.3% by mass of the colloidal acid.

Referring to fig. 1, the preparation method of the electrolyte comprises the following steps:

first, preparation of colloid mother liquor

1) Adding deionized water (the conductivity is less than or equal to 1.5 mu s/cm) into a high-speed stirring stainless steel glue preparation barrel for preparing a certain glue;

2) 500kg of colloid mother liquor with the colloid content of 15 percent is prepared each time, wherein 425kg of deionized water and 75kg of gas-phase silicon dioxide are added firstly;

3) stirring by using a high-speed stirrer, wherein the stirring time is more than 40 minutes;

4) discharging the stirred colloid mother liquor, and packaging with another colloid containing barrel;

preparation of dilute sulfuric acid

1) Opening the pure water valve until the pure water enters the acid storage barrel and the water level reaches the specified position (the transparent indicating pipe of the acid storage barrel is provided with a mark, and the water is approximately dischargedMinutes), the pure water valve is closed;

2) all acid outlet valves are closed (acid circulating valves are always kept in an open state);

3) opening a concentrated acid valve (which cannot be opened completely and is opened to half);

4) opening a circulating acid valve, and then opening an air pressure switch (the circulating acid blending machine enters an acid blending working state);

5) acid is discharged for about 2 hours, the acid liquor can reach the mark line at the top end of the transparent indicating tube of the acid storage barrel, then the valve connecting the acid storage barrel and the transparent indicating tube of the acid storage barrel is closed, and then the acid discharge valve on the transparent tube is opened;

6) after the acid liquid in the transparent tube is completely discharged, closing an acid discharge valve on the transparent tube, and opening a valve connecting the acid storage barrel and a transparent indication tube of the acid storage barrel;

7) closing the concentrated acid valve when the acid liquor reaches the mark line at the top end of the transparent indicating tube of the acid storage barrel again;

8) the whole acid preparation process works approximatelyAfter hours, detecting the density and temperature of the acid liquor (acid discharge measurement at an acid discharge valve of a circulating cooling acid distributor) to determine whether the acid liquor meets the process requirements, if not, continuing to prepare the acid liquor (if the density is higher, continuing to add water, and if the density is lower, continuing to add sulfuric acid) until the process requirements are met;

preparation of colloidal acid

1) Placing the prepared dilute sulfuric acid with the required density into a volume of 5m³The acid storage barrel (the density of the dilute sulphuric acid is necessarily larger than the required density of the colloidal acid);

2) adding 200kg of prepared colloid mother liquor, adding into the mixture with the volume of 5m and containing dilute sulfuric acid³Preparing colloidal acid in an acid storage barrel;

3) after the colloidal acid is uniformly stirred, measuring the density of the colloidal acid by using a densimeter;

4) adjusting the required colloidal acid by water or concentrated acid until the required colloidal acid density is adjusted;

preparation of new electrolyte

1) Adding diphenyl (siloxane and polysiloxane) accounting for 0.3 percent of the total weight of the liquid in the acid storage barrel into the acid storage barrel filled with the prepared colloidal acid;

2) uniformly stirring for later use.

And forming by adopting a conventional forming process to manufacture the finished lead-acid storage battery.

Example 2

This example provides an electrolyte for a lead-acid battery, which includes a colloidal acid and diphenyl groups (siloxane and polysiloxane), wherein the addition amount of the diphenyl groups (siloxane and polysiloxane) is 0.1% by mass of the colloidal acid.

The preparation method of the electrolyte comprises the following steps:

first, preparation of colloid mother liquor

1) Adding deionized water (the conductivity is less than or equal to 1.5 mu s/cm) into a high-speed stirring stainless steel glue preparation barrel for preparing a certain glue;

2) 500kg of colloid mother liquor with the colloid content of 15 percent is prepared each time, wherein 425kg of deionized water and 75kg of gas-phase silicon dioxide are added firstly;

3) stirring by using a high-speed stirrer, wherein the stirring time is more than 40 minutes;

4) discharging the stirred colloid mother liquor, and packaging with another colloid containing barrel;

preparation of dilute sulfuric acid

1) Opening the pure water valve until the water level of the pure water in the acid storage barrel reaches the specified position(the transparent indicating tube of the acid storage barrel is provided with a mark, and the water is approximately dischargedMinutes), the pure water valve is closed;

2) all acid outlet valves are closed (acid circulating valves are always kept in an open state);

3) opening a concentrated acid valve (which cannot be opened completely and is opened to half);

4) opening a circulating acid valve, and then opening an air pressure switch (the circulating acid blending machine enters an acid blending working state);

5) acid is discharged for about 2 hours, the acid liquor can reach the mark line at the top end of the transparent indicating tube of the acid storage barrel, then the valve connecting the acid storage barrel and the transparent indicating tube of the acid storage barrel is closed, and then the acid discharge valve on the transparent tube is opened;

6) after the acid liquid in the transparent tube is completely discharged, closing an acid discharge valve on the transparent tube, and opening a valve connecting the acid storage barrel and a transparent indication tube of the acid storage barrel;

7) closing the concentrated acid valve when the acid liquor reaches the mark line at the top end of the transparent indicating tube of the acid storage barrel again;

8) the whole acid preparation process works approximatelyAfter hours, detecting the density and temperature of the acid liquor (acid discharge measurement at an acid discharge valve of a circulating cooling acid distributor) to determine whether the acid liquor meets the process requirements, if not, continuing to prepare the acid liquor (if the density is higher, continuing to add water, and if the density is lower, continuing to add sulfuric acid) until the process requirements are met;

preparation of colloidal acid

1) Placing the prepared dilute sulfuric acid with the required density into a volume of 5m³The acid storage barrel (the density of the dilute sulphuric acid is necessarily larger than the required density of the colloidal acid);

2) adding 200kg of prepared colloid mother liquor, adding into the mixture with the volume of 5m and containing dilute sulfuric acid³Preparing colloidal acid in an acid storage barrel;

3) after the colloidal acid is uniformly stirred, measuring the density of the colloidal acid by using a densimeter;

4) adjusting the required colloidal acid by water or concentrated acid until the required colloidal acid density is adjusted;

preparation of new electrolyte

1) Adding diphenyl (siloxane and polysiloxane) accounting for 0.1 percent of the total weight of the liquid in the acid storage barrel into the acid storage barrel filled with the prepared colloidal acid;

2) uniformly stirring for later use.

And forming by adopting a conventional forming process to manufacture the finished lead-acid storage battery.

Comparative example 1, the same as example 1, except that no diphenyl groups (siloxane and polysiloxane) were added.

Comparative example 2, the same as example 2, except that 0.1% by weight of polydimethylsiloxane, based on the total weight of the colloidal acid, was added.

The cycle test of the batteries formed in the examples 1-2 and the comparative examples 1-2 shows that the performance of the batteries formed by using the electrolyte containing diphenyl (siloxane and polysiloxane) is obviously improved compared with the performance of the batteries formed by using the common electrolyte, the cycle test result is shown in figure 2, and the addition of polydimethylsiloxane accounting for 0.1 percent of the total weight of the colloidal acid does not obviously improve the performance of the batteries compared with the comparative example 1 and the comparative example 2; compared with the comparative example 2, the addition of diphenyl (siloxane and polysiloxane) with equal mass is more beneficial to the improvement of the battery performance than the addition of polydimethylsiloxane; from the comparison of example 1 with example 2, it was found that the addition of 0.3% by weight of diphenyl (siloxane and polysiloxane) based on the total weight of the colloidal acid is more advantageous in improving the battery performance than the addition of 0.1% by weight of diphenyl (siloxane and polysiloxane) based on the total weight of the colloidal acid.

Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes in the embodiments and/or modifications of the invention can be made, and equivalents and modifications of some features of the invention can be made without departing from the spirit and scope of the invention.