Positive electrode lead paste additive of lead storage power battery and application of positive electrode lead paste additive

Abstract

The invention relates to the field of lead storage batteries, and discloses a lead storage power battery positive electrode lead paste additive and application thereof. The additive is composed of a tin-antimony compound, 4BS and graphite, the addition amount of the tin-antimony compound is 0.1%-0.5% of the weight of lead powder used in the positive electrode of the lead storage power battery, the addition amount of the 4BS is 0.5%-2% of the weight of the lead powder used in the positive electrode of the lead storage power battery, and the addition amount of the graphite is 0.1%-0.3% of the weight of the lead powder used in the positive electrode of the lead storage power battery. The additive disclosed by the invention is used in the positive lead plaster of the lead storage power battery, and can improve the porosity of a polar plate, improve the charge-discharge efficiency and the initial capacity of the battery and guarantee the cycle service life of the battery at the same time.

Description

Technical Field

[0001] The invention belongs to the technical field of lead-acid battery materials, and in particular relates to a positive electrode lead paste additive for a lead-acid power battery and an application thereof. Background Art

[0002] The performance of lead-acid batteries is subject to the positive electrode. Adding appropriate additives to the positive electrode active material can improve the conductivity, porosity, activity, and binding force between PbO2 particles, inhibit grid corrosion, and improve the utilization rate of active materials or extend their life. Additives also affect the precipitation overpotential of O2 on the PbO2 electrode and the ability of PbSO4 to oxidize to PbO2, thereby affecting the self-discharge and charge-discharge performance of the battery. The specific surface area of ​​the lead paste, the mechanical strength of the plate, and the stability of the active material are the key factors that determine the service life of the battery. The crystal form and porosity of the lead paste can determine the battery charge-discharge efficiency and initial capacity. In order to improve and enhance the performance of lead-acid power batteries, additives are often added during the paste. At present, the most common additives for the positive lead paste of lead-acid power batteries are mainly stannous sulfate and antimony trioxide. After adding these two substances, the lead paste components are mainly PbO and 3BS (tribasic lead sulfate). Due to the presence of 3BS, the lead paste particles are small, the crystal form is irregular, the porosity is low, and the initial performance of the battery is slightly poor. A common method to improve the particle size and crystal form of lead paste is to add 4BS (tetrabasic lead sulfate) seeds, so that the lead powder can be converted into 4BS with regular crystal form and coarse particles in large quantities during the process of mixing and curing the paste, thereby increasing the utilization rate of active substances in the lead paste and improving the initial performance of the battery. During the use of conventional formulas, stannous sulfate and antimony trioxide significantly inhibit the 4BS seeds, and the lead powder can hardly be converted into 4BS during mixing and curing. However, tin and antimony are important additives to ensure the life of the battery and are indispensable. To solve this problem, adding additives that do not inhibit 4BS seeds can not only improve the initial performance of the battery, but also ensure the service life of the battery. Summary of the invention

[0003] The purpose of the present invention is to solve the above-mentioned deficiencies of the prior art and provide a lead-acid battery additive that does not inhibit 4BS seed crystals, so as to improve the initial capacity of the battery and ensure the battery life. The present invention also provides the application of the battery additive.

[0004] The technical solution adopted by the present invention is as follows:

[0005] A positive electrode lead paste additive for a lead-acid battery, the additive consisting of a tin-antimony compound, 4BS and graphite, wherein the tin-antimony compound is added in an amount of 0.1% to 0.5% by weight of lead powder used in the positive electrode of the lead-acid battery, the 4BS is added in an amount of 0.5% to 2% by weight of lead powder used in the positive electrode of the lead-acid battery, and the graphite is added in an amount of 0.1% to 0.3% by weight of lead powder used in the positive electrode of the lead-acid battery.

[0006] The preparation method of the tin antimony compound of the present invention is as follows:

[0007] (1) Prepare an antimony trichloride solution with a molar concentration of 0.5 mol / L~1 mol / L and a sodium stannate solution with a molar concentration of 0.5 mol / L~1 mol / L, and the molar ratio of the antimony trichloride solution to the sodium stannate solution is 2:3;

[0008] (2) Add 1% to 2% sodium dodecylbenzene sulfonate by mass to the sodium stannate solution, then slowly add antimony trichloride solution at 30 to 50 °C. o C, and stirred at constant temperature for 3-5 hours;

[0009] (3) After the reaction is completed, stirring is stopped, the phases are allowed to stand and separated, the brine phase is removed, and the solid phase is washed with water, filtered, and dried to obtain a tin antimony compound.

[0010] The application method of the positive electrode lead paste additive for lead-acid power battery is to add the lead paste additive to the raw materials for preparing the positive electrode of the lead-acid power battery, stir evenly to obtain the positive electrode lead paste, and evenly apply the positive electrode lead paste on the positive electrode grid of the lead-acid power battery.

[0011] The present invention uses tin antimony compound, 4BS and graphite as positive lead paste additives for lead-acid power batteries. The graphite in the additive can improve the conductivity of the active material, and the tin antimony compound does not inhibit the 4BS crystal seed, so that most of the PbO in the solidified lead powder can be converted into large particles of 4BS to form a lead paste with regular crystal form, thereby improving the charging and discharging efficiency and the initial capacity of the battery. The presence of the tin antimony compound can increase the specific surface area of ​​the lead paste, stabilize the active material, and ensure the service life of the battery. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Figure 1 This is the energy spectrum of the tin antimony compound obtained in Example 1. DETAILED DESCRIPTION

[0013] The present invention is further described below in conjunction with the embodiments. The embodiments listed are only partial embodiments of the present invention and are not intended to limit the scope of protection of the present invention.

[0014] Example 1

[0015] A lead paste additive for positive electrode of lead-acid power battery, comprising 1.5g of tin-antimony compound, 1.5g of graphite, and 7.5g of 4BS. The preparation method of the tin-antimony compound is as follows:

[0016] (1) preparing an antimony trichloride solution with a molar concentration of 0.8 mol / L and a sodium stannate solution with a molar concentration of 0.8 mol / L, wherein the molar ratio of the antimony trichloride solution to the sodium stannate solution is 2:3;

[0017] (2) Add 1% sodium stannate by mass of sodium dodecylbenzene sulfonate to the sodium stannate solution, then slowly add antimony trichloride solution dropwise at 40 o C, and stirred at constant temperature for 4 h;

[0018] (3) After the reaction is completed, stirring is stopped, the phases are allowed to stand and separated, the brine phase is removed, and the solid phase is washed with water, filtered, and dried to obtain a tin antimony compound.

[0019] The structural characterization of the tin antimony compound obtained in this example is shown in Figure 1 The energy spectrum of tin antimony compounds is shown.

[0020] The application method of the obtained lead-acid battery positive electrode lead paste additive is to add the lead paste additive into the raw materials for preparing the positive electrode of the lead-acid battery, stir evenly to obtain the positive electrode lead paste, and evenly apply the positive electrode lead paste on the positive electrode grid of the lead-acid battery.

[0021] Add 1500g lead powder, 1.5g fiber, 1.5g tin antimony compound, 1.5g graphite, 7.5g 4BS to the lead paste and paste machine, the density is 1.40g / cm 3 120g of sulfuric acid and 171g of pure water were mechanically stirred for 50min to obtain positive lead paste. The positive lead paste was evenly applied to the positive grid, and the positive plate was obtained by rolling, curing and drying according to the existing positive plate production process. The positive plate was assembled into a 2V20Ah single cell battery with the negative plate, diaphragm and sulfuric acid electrolyte using the existing lead-acid battery assembly process. After the battery was formed, the initial capacity and cycle life of the battery were tested according to GB / T 22199.1-2017 "Valve-regulated lead-acid batteries for electric power-assisted vehicles Part 1: Technical conditions".

[0022] Example 2

[0023] A lead paste additive for positive electrode of lead-acid power battery, comprising 3g of tin-antimony compound, 2.5g of graphite, and 15g of 4BS. The preparation method of the tin-antimony compound is as follows:

[0024] (1) preparing an antimony trichloride solution with a molar concentration of 1 mol / L and a sodium stannate solution with a molar concentration of 0.5 mol / L, wherein the molar ratio of the antimony trichloride solution to the sodium stannate solution is 2:3;

[0025] (2) Add 2% sodium dodecylbenzene sulfonate by mass to the sodium stannate solution, then slowly add antimony trichloride solution dropwise at 50 o C, and stirred at constant temperature for 3 h;

[0026] (3) After the reaction is completed, stirring is stopped, the phases are allowed to stand and separated, the brine phase is removed, and the solid phase is washed with water, filtered, and dried to obtain a tin antimony compound.

[0027] Add 1500g lead powder, 1.5g fiber, 3g tin antimony compound, 2.5g graphite, 15g 4BS to the lead paste and paste machine, the density is 1.40g / cm 3 120g of sulfuric acid and 171g of pure water were mechanically stirred for 50 minutes to obtain positive lead paste. The lead paste was evenly applied to the positive grid, and the positive plate was obtained by rolling, curing and drying through the existing positive plate production process. The positive plate was assembled into a 2V20Ah single cell battery using the existing lead-acid battery assembly process with the negative plate, diaphragm and sulfuric acid electrolyte. After the battery was formed, the initial capacity and cycle life of the battery were tested according to GB / T 22199.1-2017 "Valve-regulated lead-acid batteries for electric power-assisted vehicles Part 1: Technical conditions".

[0028] Example 3

[0029] A lead paste additive for positive electrode of a lead-acid battery, comprising 4.5g of tin-antimony compound, 3g of graphite, and 22.5g of 4BS. The preparation method of the tin-antimony compound is as follows:

[0030] (1) preparing an antimony trichloride solution with a molar concentration of 1 mol / L and a sodium stannate solution with a molar concentration of 1 mol / L, wherein the molar ratio of the antimony trichloride solution to the sodium stannate solution is 2:3;

[0031] (2) Add sodium dodecylbenzene sulfonate (1.4% by mass of sodium stannate) to the sodium stannate solution, then slowly add antimony trichloride solution dropwise at 30 o C, and stirred at constant temperature for 5 h;

[0032] (3) After the reaction is completed, stirring is stopped, the phases are allowed to stand and separated, the brine phase is removed, and the solid phase is washed with water, filtered, and dried to obtain a tin antimony compound.

[0033] Add 1500g lead powder, 1.5g fiber, 4.5g tin antimony compound, 3g graphite, 22.5g 4BS to the lead paste and paste machine, the density is 1.40g / cm 3 120g of sulfuric acid and 171g of pure water were mechanically stirred for 50 minutes to obtain positive lead paste. The lead paste was evenly applied to the positive grid, and the positive plate was obtained by rolling, curing and drying through the existing positive plate production process. The positive plate was assembled into a 2V20Ah single cell battery using the existing lead-acid battery assembly process with the negative plate, diaphragm and sulfuric acid electrolyte. After the battery was formed, the initial capacity and cycle life of the battery were tested according to GB / T 22199.1-2017 "Valve-regulated lead-acid batteries for electric power-assisted vehicles Part 1: Technical conditions".

[0034] Example 4

[0035] A lead paste additive for positive electrode of a lead-acid battery is prepared by the following method:

[0036] (1) preparing an antimony trichloride solution with a molar concentration of 0.5 mol / L and a sodium stannate solution with a molar concentration of 0.5 mol / L, wherein the molar ratio of the antimony trichloride solution to the sodium stannate solution is 2:3;

[0037] (2) Add sodium dodecylbenzene sulfonate (1.7% by mass of sodium stannate) to the sodium stannate solution, then slowly add antimony trichloride solution dropwise at 45 o C, and stirred at constant temperature for 4 h;

[0038] (3) After the reaction is completed, stirring is stopped, the phases are allowed to stand and separated, the brine phase is removed, and the solid phase is washed with water, filtered, and dried to obtain a tin antimony compound.

[0039] Add 1500g lead powder, 1.5g fiber, 7.5g tin antimony compound, 4.5g graphite, 30g 4BS to the lead paste and paste machine, the density is 1.40g / cm 3 120g of sulfuric acid and 171g of pure water were mechanically stirred for 50 minutes to obtain positive lead paste. The lead paste was evenly applied to the positive grid, and the positive plate was obtained by rolling, curing and drying through the existing positive plate production process. The positive plate was assembled into a 2V20Ah single cell battery using the existing lead-acid battery assembly process with the negative plate, diaphragm and sulfuric acid electrolyte. After the battery was formed, the initial capacity and cycle life of the battery were tested according to GB / T 22199.1-2017 "Valve-regulated lead-acid batteries for electric power-assisted vehicles Part 1: Technical conditions".

[0040] Comparative Example

[0041] According to the conventional formula of the industry, 1500g lead powder, 1.5g fiber, 1.5g antimony trioxide, and 1.5g stannous sulfate are added to the lead paste and paste machine, and the density is 1.40g / cm 3 120g of sulfuric acid and 171g of pure water were mechanically stirred for 50 minutes to obtain positive lead paste. The lead paste was evenly applied to the positive grid, and the positive plate was obtained by rolling, curing and drying through the existing positive plate production process. The positive plate was assembled into a 2V20Ah single cell battery using the existing lead-acid battery assembly process with the negative plate, diaphragm and sulfuric acid electrolyte. After the battery was formed, the initial capacity and cycle life of the battery were tested according to GB / T 22199.1-2017 "Valve-regulated lead-acid batteries for electric power-assisted vehicles Part 1: Technical conditions".

[0042] The phase compositions of the lead pastes prepared in the above-mentioned embodiments and comparative examples are shown in Table 1.

[0043] Table 1 Phase composition of lead paste

[0044]

[0045] The performance test results of the lead-acid batteries prepared in the above embodiments and comparative examples are shown in Table 2.

[0046] Table 2 Lead-acid battery performance test results

[0047]

[0048] It can be seen from Table 1 and Table 2 that the lead-acid battery to which the positive electrode lead paste additive for lead-acid power batteries of the present invention is added is mainly composed of lead oxide and 4BS, while the lead paste of the comparative example is mainly composed of lead oxide and 3BS, compared with the comparative example having a conventional formula without adding the additive. The lead paste of the present invention can significantly improve the initial capacity of the battery, and the battery cycle life can also reach the level of the conventional formula.

[0049] The raw materials used in the present invention can all be obtained commercially.

Claims

1. A lead paste additive for positive electrode of lead-acid battery, characterized in that: The additive consists of tin antimony compound, 4BS and graphite, wherein the tin antimony compound is added in an amount of 0.1% to 0.5% by weight of the lead powder used in the positive electrode of the lead-acid battery, the 4BS is added in an amount of 0.5% to 2% by weight of the lead powder used in the positive electrode of the lead-acid battery, and the graphite is added in an amount of 0.1% to 0.3% by weight of the lead powder used in the positive electrode of the lead-acid battery.

2. A lead paste additive for positive electrode of lead-acid power battery according to claim 1, characterized in that: The preparation method of the tin antimony compound is as follows: (1) Prepare an antimony trichloride solution with a molar concentration of 0.5 mol / L~1 mol / L and a sodium stannate solution with a molar concentration of 0.5 mol / L~1 mol / L, and the molar ratio of the antimony trichloride solution to the sodium stannate solution is 2:3; (2) Add 1% to 2% sodium dodecylbenzene sulfonate by mass to the sodium stannate solution, then slowly add antimony trichloride solution at 30 to 50 °C. o C, and stirred at constant temperature for 3-5 hours; (3) After the reaction is completed, stirring is stopped, the phases are allowed to stand and separated, the brine phase is removed, and the solid phase is washed with water, filtered, and dried to obtain a tin antimony compound.

3. The use of a lead paste additive for a positive electrode of a lead-acid power battery according to claim 1 or 2, wherein the lead paste additive is added to a raw material for preparing a positive electrode of a lead-acid power battery, stirred evenly to obtain a positive electrode lead paste, and the positive electrode lead paste is evenly applied to the positive electrode grid of the lead-acid power battery.

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