Negative electrode lead paste of lead-sodium storage battery and preparation method of negative electrode lead paste

Abstract

The invention discloses negative electrode lead paste of a lead-sodium storage battery in the technical field of storage batteries. The negative electrode lead paste comprises the following materials in parts by weight: 100 parts of lead oxide powder, 6-12 parts of sulfuric acid and 11-20 parts of deionized water. The fertilizer is prepared from the following components in parts by weight: 0.05 to 0.07 part of short fiber, 0.3 to 0.9 part of humic acid, 0.1 to 0.3 part of sodium lignosulfonate, 0.06 to 1 part of silicon dioxide, 0.8 to 1.6 parts of barium sulfate, 0.1 to 0.5 part of sodium sulfate, 0.04 to 0.1 part of ammonium persulfate, 0.06 to 0.1 part of vanillin, 0.2 to 0.4 part of colla corii asini and 0.2 to 0.4 part of mixed carbon material. The stability of the additive and the mixing uniformity are effectively improved, the low temperature resistance of the battery is improved, and the service life of the battery is prolonged.

Description

Technical Field

[0001] The invention relates to the technical field of storage batteries, in particular to a lead-sodium storage battery. Background Art

[0002] The traditional negative electrode lead paste formula is to use a paste mixing machine to dry mix lead oxide powder, sulfuric acid, deionized water, short fibers and additives in a certain proportion, and then mix them with water and acid to make lead paste. Negative electrode additives have the functions of improving charge acceptance, extending life, improving low-temperature discharge performance, and inhibiting sulfation. However, the uniformity of the mixing of additives in the lead paste affects its performance. In addition, organic expanders such as sodium lignin sulfonate can improve low-temperature working ability and improve the morphology of lead sulfate crystals. However, after sodium lignin sulfonate is added to the negative electrode, its stability is poor and it will dissolve during the charging and discharging process, and its effect will gradually diminish. The above problems cause the battery to have poor low-temperature performance and short life. Therefore, a lead-sodium battery negative electrode lead paste and a preparation method thereof are needed to solve the above problems. Summary of the invention

[0003] In view of the deficiencies in the prior art, the present invention provides a lead paste for negative electrode of a lead-sodium battery, which can effectively improve the low temperature resistance and life of the battery.

[0004] The object of the present invention is achieved in this way: a lead paste for negative electrode of a lead-sodium storage battery, comprising the following materials in parts by weight: 100 parts of lead oxide powder, 6-12 parts of sulfuric acid, 11-20 parts of deionized water; 0.05-0.07 parts of short fibers, 0.3-0.9 parts of humic acid, 0.1-0.3 parts of sodium lignin sulfonate, 0.06-1 parts of silicon dioxide, 0.8-1.6 parts of barium sulfate, 0.1-0.5 parts of sodium sulfate, 0.04-0.1 parts of ammonium persulfate, 0.06-0.1 parts of vanillin, 0.2-0.4 parts of glue, and 0.2-0.4 parts of mixed carbon materials.

[0005] Furthermore, the lead oxide powder has an oxidation degree of 72-80% and a particle size of ≤5 μm.

[0006] Furthermore, the particle size of the silicon dioxide particles is ≤30 μm.

[0007] Furthermore, the carbon material includes acetylene black, carbon black and graphene.

[0008] A method for preparing a negative electrode lead paste for a lead-sodium battery comprises the following steps: S1. According to the proportion, humic acid, lignin or sodium lignin sulfonate are added to deionized water and stirred to dissolve, and a set proportion of silicon dioxide particles are added to the prepared solution, and then the solution is decompressed and pressurized, and the mixture is fully mixed and dried to obtain a mixture A; S2. Add barium sulfate and sodium sulfate in proportion to mixture A into a ball mill for mixing to obtain mixture B; S3. Dissolve tannin extract in deionized water in proportion to prepare a tannin extract solution; S4. Add mixture B, short fibers, ammonium persulfate, vanillin, and mixed carbon materials into a paste mixer for dry mixing with lead powder, and then add the tannin extract solution, the remaining deionized water, and sulfuric acid respectively for water mixing and acid mixing to obtain the negative electrode lead paste.

[0009] Further, in S1, the stirring time for stirring and dissolving > 10 min. After adding silica particles in a set proportion to the prepared solution, reduce the pressure to -0.1 to -0.3 MPa, then increase the pressure to 0.1 MPa, fully mix and then perform drying treatment. The drying temperature ≥ 60 °C and the time > 5 h.

[0010] Further, in S2, the rotation speed of the ball mill is 200 - 300 rpm and the mixing time is 0.5 - 1 h.

[0011] Further, the dry mixing time in S4 is 5 - 12 min, and water mixing and acid mixing are respectively carried out with deionized water and sulfuric acid. The water addition time is 1 - 3 min, the water mixing time is 5 - 10 min, the density of the sulfuric acid is 1.4 g / cm 3 , the acid addition time is 15 - 20 min, and the acid mixing time is 5 - 10 min.

[0012] Compared with the prior art, the beneficial effects of the present invention are as follows: The present invention can effectively improve the stability of the additive and the mixing uniformity. Among them, mixture A has a more stable structure. Humic acid and sodium lignosulfonate are immersed in silica particles through pressure increase and decrease, solving the instability problem of sodium lignosulfonate. During the charge and discharge of the battery, sodium lignosulfonate in mixture A is not easily dissolved, and at the same time, under the action of humic acid and silica, it has better low-temperature performance and also has an excellent effect on inhibiting hydrogen evolution at the negative electrode; The mixed carbon material can construct a better conductive network, improving the conductivity and the activity of ion migration at low temperatures; Further, add mixture A, barium sulfate, and sodium sulfate into a ball mill for mixing to obtain mixture B, realizing physical embedding, with uniform powder particle size, ensuring that the ground mixture can be evenly distributed in the active substances during pasting, enabling the performance of each component material in the mixture to be fully exerted, and under the combined action of other additives such as ammonium persulfate, vanillin, and tannin extract, thereby improving the stability, low-temperature performance, and service life of the battery. Description of the Drawings

[0013] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are only the embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on the provided drawings.

[0014] Figure 1 It is a schematic diagram of the discharge of the embodiment of the present invention and the comparative example applied to the battery in a low-temperature state.

[0015] Figure 2 It is a schematic diagram of the discharge of the embodiment of the present invention and the comparative example applied to the battery in a normal-temperature state.

[0016] Figure 3 It is a cyclic life curve graph of the embodiment of the present invention and the comparative example applied to the battery. Detailed implementation manners

[0017] The following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.

[0018] Embodiment 1 A negative lead paste for a lead-sodium battery includes the following materials in parts by weight: 100 parts of lead oxide powder, 6 parts of sulfuric acid, 11 parts of deionized water, 0.05 part of short fiber, 0.3 part of humic acid, 0.1 part of sodium lignosulfonate, 0.06 part of silicon dioxide, 0.8 part of barium sulfate, 0.1 part of sodium sulfate, 0.04 part of ammonium persulfate, 0.06 part of vanillin, 0.2 part of tannin extract, and 0.2 part of mixed carbon material.

[0019] Specifically, the oxidation degree of the lead powder is 72%, the particle size is 3 - 4 μm, the silicon dioxide particles are ≤ 30 μm, and the carbon material is 0.1 part of acetylene black, 0.05 part of carbon black, and 0.05 part of graphene.

[0020] A method for preparing a negative lead paste for a lead-sodium battery includes the following steps: S1. According to the ratio, add 0.3 part of humic acid and 0.1 part of sodium lignosulfonate to 1 part of deionized water and stir to dissolve. The stirring time is 20 min. After adding 0.06 part of silicon dioxide particles to the prepared solution, reduce the pressure to -0.1 MPa, and the pressure reduction time is 30 min. Then increase the pressure to 0.1 MPa, fully mix and then perform a drying treatment. The drying temperature is 90 °C and the time is 24 h to obtain mixture A; S2. Add 0.8 parts of barium sulfate and 0.1 part of sodium sulfate in proportion to mixture A into a ball mill for mixing. The rotation speed of the ball mill is 300 rpm, and the premixing time is 0.5 h; S3. Dissolve 0.2 part of tannin extract in 0.8 part of deionized water to prepare a tannin extract solution; S4. Add 0.05 part of short fiber, 0.04 part of ammonium persulfate, 0.06 part of vanillin, 0.1 part of acetylene black, 0.05 part of carbon black, and 0.05 part of graphene to mixture B and dry-mix them in a paste mixer with lead powder. The dry-mixing time is 8 min. Then add 1 part of the tannin extract solution, the remaining 9 parts of deionized water, and 6 parts of sulfuric acid respectively for water mixing and acid mixing. The water addition time is 1.5 min, the water mixing time is 6 min, the density of sulfuric acid is 1.4 g / cm3, the acid addition time is 17 min, and the acid mixing time is 5 min, thereby obtaining the negative electrode lead paste.

[0021] Example 2 A negative electrode lead paste for a lead-sodium storage battery, comprising the following materials in parts by weight: 100 parts of lead oxide powder, 9 parts of sulfuric acid, 15 parts of deionized water, 0.06 part of short fiber, 0.6 part of humic acid, 0.2 part of sodium lignosulfonate, 0.08 part of silicon dioxide, 1.2 parts of barium sulfate, 0.3 part of sodium sulfate, 0.07 part of ammonium persulfate, 0.08 part of vanillin, 0.3 part of tannin extract, and 0.3 part of mixed carbon material.

[0022] Specifically, the oxidation degree of the lead powder is 74%, the particle size is 4 - 5 μm, the silicon dioxide particles are ≤ 30 μm, and the carbon material is 0.2 part of acetylene black, 0.05 part of carbon black, and 0.05 part of graphene.

[0023] A preparation method of a negative electrode lead paste for a lead-sodium storage battery, comprising the following steps: S1. Add 0.6 part of humic acid and 0.2 part of sodium lignosulfonate in proportion to 2 parts of deionized water and stir to dissolve. The stirring time is 20 min. After adding 0.08 part of silicon dioxide particles to the prepared solution, reduce the pressure to -0.1 MPa, and the pressure reduction time is 45 min. Then increase the pressure to 0.1 MPa, fully mix and then perform drying treatment. The drying temperature is 75 °C, and the time is 36 h to obtain mixture A; S2. Add 1.2 parts of barium sulfate and 0.3 part of sodium sulfate in proportion to mixture A into a ball mill for mixing and grinding. The rotation speed of the ball mill is 200 rpm, and the premixing time is 1 h; S3. Dissolve 0.3 part of tannin extract in 1.2 parts of deionized water to prepare a tannin extract solution; S4. Add 0.06 parts of short fibers, 0.07 parts of ammonium persulfate, 0.08 parts of vanillin, 0.2 parts of acetylene black, 0.05 parts of carbon black, and 0.05 parts of graphene to mixture B, and add them to a paste mixer to dry-mix with lead powder. The dry-mixing time is 6 minutes. Then add 1.5 parts of tannin solution, 11.8 parts of the remaining deionized water, and 9 parts of sulfuric acid respectively for water mixing and acid mixing. The water addition time is 1 minute, the water mixing time is 6 minutes, the density of sulfuric acid is 1.4 g / cm3, the acid addition time is 16 minutes, and the acid mixing time is 6 minutes, thus obtaining the negative electrode lead paste.

[0024] Example 3 A negative electrode lead paste for a lead-sodium storage battery, comprising the following materials in parts by weight: 100 parts of lead oxide powder, 12 parts of sulfuric acid, 20 parts of deionized water; 0.07 parts of short fibers, 0.9 parts of humic acid, 0.3 parts of sodium lignosulfonate, 1 part of silicon dioxide, 1.6 parts of barium sulfate, 0.5 parts of sodium sulfate, 0.1 parts of ammonium persulfate, 0.1 parts of vanillin, 0.4 parts of tannin, and 0.4 parts of mixed carbon materials.

[0025] Specifically, the oxidation degree of lead powder is 72%, the particle size is 3 - 4 μm, the silicon dioxide particles are ≤ 30 μm, and the carbon materials are 0.2 parts of acetylene black, 0.15 parts of carbon black, and 0.05 parts of graphene.

[0026] A method for preparing a negative electrode lead paste for a lead-sodium storage battery, comprising the following steps: S1. According to the ratio, add 0.9 parts of humic acid and 0.3 parts of sodium lignosulfonate to 3 parts of deionized water and stir to dissolve. The stirring time is 15 minutes. After adding 1 part of silicon dioxide particles to the prepared solution, reduce the pressure to -0.15 MPa, and the pressure reduction time is 20 minutes. Then increase the pressure to 0.1 MPa, fully mix and perform drying treatment. The drying temperature is 70 °C and the time is 40 h to obtain mixture A; S2. Add 1.6 parts of barium sulfate and 0.5 parts of sodium sulfate in accordance with the ratio to mixture A and add them to a ball mill for mixing and grinding. The rotation speed of the ball mill is 250 rpm, and the premixing time is 0.5 h; S3. Dissolve 0.4 parts of tannin in 1.6 parts of deionized water to prepare a tannin solution; S4. Add 0.07 parts of short fibers, 0.1 parts of ammonium persulfate, 0.1 parts of vanillin, 0.2 parts of acetylene black, 0.15 parts of carbon black, and 0.05 parts of graphene to mixture B, and add them to a paste mixer to dry-mix with lead powder. The dry-mixing time is 10 minutes. Then add 2 parts of tannin solution, 15.4 parts of the remaining deionized water, and 12 parts of sulfuric acid respectively for water mixing and acid mixing. The water addition time is 1 minute, the water mixing time is 5 minutes, the density of sulfuric acid is 1.4 g / cm3, the acid addition time is 15 minutes, and the acid mixing time is 5 minutes, thus obtaining the negative electrode lead paste.

[0027] Comparative example A lead-acid battery negative electrode lead paste, comprising the following materials in parts by weight: 100 parts of lead oxide powder, 9 parts of sulfuric acid, 12 parts of deionized water; 0.06 part of short fiber, 0.6 part of humic acid, 0.2 part of sodium lignosulfonate, 1.2 parts of barium sulfate, 0.2 part of acetylene black, and 0.1 part of carbon black.

[0028] A preparation method of a lead-acid battery negative electrode lead paste, adding 0.06 part of short fiber, 0.6 part of humic acid, 0.2 part of sodium lignosulfonate, 1.1 part of barium sulfate, 0.2 part of acetylene black, and 0.1 part of carbon black into a paste mixer and dry mixing with lead powder for 6 min, and respectively performing water mixing and acid mixing with 12 parts of deionized water and 9 parts of sulfuric acid. The water addition time is 1 min, the water mixing time is 6 min, the sulfuric acid density is 1.4 g / cm3, the acid addition time is 16 min, and the acid mixing time is 6 min, thereby obtaining the negative electrode lead paste.

[0029] The above negative electrode lead paste Examples 1, 2, 3 and Comparative Examples are made into negative electrode plates. It should be noted that the preparation process of the negative electrode plates is the existing conventional process and will not be elaborated in this solution. Under the condition that the plate ratio, separator, and battery case are completely the same, acid filling and forming are carried out to make a storage battery. The following test methods are adopted: 1. 10-hour rate capacity test: After the fully charged storage battery is charged, within 1 h to 24 h, discharge with a current of I 10 (A), and the temperature around the storage battery is maintained between 20 and 25 °C. During the discharge time, the change in the current value should not be greater than 1%. When the single-cell voltage of the storage battery reaches 1.80 V, stop discharging and record the discharge time, and calculate the discharge capacity.

[0030] 2. -40 °C low-temperature capacity test: Place the fully charged storage battery in an environment of -40 °C ± 2 °C and let it stand for 20 h, and discharge the storage battery with a current of I 10 (A). During the discharge process, the temperature around the storage battery is maintained between -40 °C ± 2 °C, and the change in the current value should not be greater than 1%. When the single-cell voltage of the storage battery reaches 1.80 V, stop discharging and record the discharge time, and calculate the discharge capacity.

[0031] 3. Cycle life test: The temperature around the storage battery is maintained between 20 and 25 °C. a) Discharge with a current of I 10 (A) until the single-cell voltage of the storage battery reaches 1.80 V; b) Limit the voltage to 2.35 V / cell and charge with 2.5I10 (A) for 12 h; c) Repeat steps a) and b). (When the discharge time in step a is less than 8 hours, the life test is terminated) As can be seen from the above, as Figures 1 - 3As shown, by comparing the solutions of Examples 1 to 3 with the comparative examples, when the 10-hour rate capacity is close, better low-temperature performance and cycle life can be obtained by using the lead paste and manufacturing method of the present invention. The components of the present invention are simple, the production cost is relatively low, the manufactured battery has good low-temperature resistance and cycle life, and has a wide range of applications.

[0032] The descriptions of the above embodiments are only used to help understand the method and its core idea of the present invention. It should be noted that for those of ordinary skill in the art of this technology, without departing from the principle of the present invention, several improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

Claims

1. A lead paste for negative electrode of a lead-sodium battery, characterized in that: Including the following materials by weight: 100 parts of lead oxide powder, 6-12 parts of sulfuric acid, 11-20 parts of deionized water; 0.05-0.07 parts of short fibers, 0.3-0.9 parts of humic acid, 0.1-0.3 parts of sodium lignin sulfonate, 0.06-1 parts of silicon dioxide, 0.8-1.6 parts of barium sulfate, 0.1-0.5 parts of sodium sulfate, 0.04-0.1 parts of ammonium persulfate, 0.06-0.1 parts of vanillin, 0.2-0.4 parts of glue, and 0.2-0.4 parts of mixed carbon materials.

2. A lead paste for negative electrode of a lead-sodium battery according to claim 1, characterized in that: The lead oxide powder has an oxidation degree of 72-80% and a particle size of ≤5 μm.

3. A lead paste for negative electrode of a lead-sodium storage battery according to claim 1 or 2, characterized in that: The silica particles have a particle size of ≤30 μm.

4. A lead paste for negative electrode of a lead-sodium storage battery according to claim 1 or 2, characterized in that: The carbon material includes acetylene black, carbon black and graphene.

5. A method for preparing a negative electrode lead paste for a lead-sodium storage battery as claimed in any one of claims 1 to 4, characterized in that: The following steps are involved: S1. Add humic acid and sodium lignin sulfonate to deionized water according to the proportion, stir and dissolve, add silicon dioxide particles in a set proportion to the prepared solution, reduce pressure and increase pressure, mix thoroughly and dry to obtain a mixture A; S2, adding mixture A and barium sulfate and sodium sulfate in proportion into a ball mill and mixing them to obtain mixture B; S3, adding the adhesive to deionized water to dissolve according to the proportion to prepare an adhesive solution; S4. Add mixture B, short fibers, ammonium persulfate, vanillin, and mixed carbon materials into a paste mixer and dry mix with lead powder. Then, add the glue solution and the remaining deionized water and sulfuric acid respectively for water mixing and acid mixing to prepare a negative electrode lead paste.

6. The method for preparing a negative electrode lead paste for a lead-sodium storage battery according to claim 5, characterized in that: The stirring time for the stirring and dissolving in S1 is greater than 10 minutes. After adding a set proportion of silicon dioxide particles to the prepared solution, the pressure is reduced to -0.1~-0.3MPa, and then the pressure is increased to 0.1MPa. After sufficient mixing, the solution is dried at a temperature of ≥60°C and the time is greater than 5h.

7. The method for preparing a negative electrode lead paste for a lead-sodium storage battery according to claim 5 or 6, characterized in that: The ball mill speed in S2 is 200~300rpm, and the mixing time is 0.5~1h.

8. The method for preparing a negative electrode lead paste for a lead-sodium storage battery according to claim 5 or 6, characterized in that: The dry mixing time in S4 is 5-12 minutes, and the adhesive solution and the remaining deionized water and sulfuric acid are mixed with water and acid respectively. The water adding time is 1-3 minutes, and the water mixing time is 5-10 minutes. The density of the sulfuric acid is 1.4 g / cm 3 , acid adding time is 15~20min, and acid mixing time is 5~10min.

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