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

Abstract

The invention discloses a lead-carbon storage battery negative electrode lead paste in the technical field of storage batteries. The lead-carbon storage battery negative electrode lead paste comprises the following materials in parts by weight: 0.2-0.6 part of a biomass derived carbon material, 6-12 parts of sulfuric acid and 12-20 parts of deionized water. The fertilizer is prepared from, by weight, 0.08-0.1 part of short fibers, 0.1-0.3 part of humic acid, 0.2-0.4 part of sodium lignosulfonate, 0.4-0.8 part of carboxymethylcellulose, 0.6-1 part of barium sulfate and 100 parts of lead oxide powder. The lead-carbon battery provided by the invention has excellent battery performance and long service life, and meanwhile, the preparation cost of the battery is effectively reduced.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of storage batteries, in particular to a lead-carbon storage battery. BACKGROUND

[0002] At present, lead-acid storage batteries are widely used in the fields of electric power storage, automobile start-stop, electric transportation, etc., and their performance is limited by the microstructure and material composition of the negative plate. The preparation of traditional negative lead paste usually relies on commercial carbon materials (such as acetylene black, graphite, etc.) as conductive additives to improve the electrical conductivity, inhibit sulfation, and improve the charge acceptance. However, the preparation cost of commercial carbon materials is high, and the source is limited, which seriously restricts the large-scale low-cost application of lead-acid batteries. Therefore, there is an urgent need for a widely available, low-cost and high-performance carbon material to replace the traditional additive commercial carbon and improve the overall performance of the battery. SUMMARY

[0003] In view of the deficiencies in the prior art, the present application provides a lead-carbon storage battery negative lead paste and a preparation method thereof, which uses cheap biomass-derived carbon material to replace expensive commercial carbon; at the same time, the doping of heteroatom (N, O, etc.) functional groups in the biomass-derived carbon improves the hydrogen evolution potential, inhibits irreversible sulfation, and effectively improves the performance and life of the battery.

[0004] The purpose of the present application is achieved by a lead-carbon storage battery negative lead paste, which comprises the following materials by weight: 0.2-0.6 parts of biomass-derived carbon material, 6-12 parts of sulfuric acid, 12-20 parts of deionized water, 0.08-0.1 parts of short fibers, 0.1-0.3 parts of humic acid, 0.2-0.4 parts of sodium lignosulfonate, 0.4-0.8 parts of carboxymethyl cellulose, 0.6-1 parts of barium sulfate, and 100 parts of lead oxide powder.

[0005] Further, the preparation method of the biomass-derived carbon material comprises the following steps: First, prepare the raw materials, prepare the seaweed, deionized water, anhydrous ethanol, potassium hydroxide, hydrochloric acid and inert gas; Secondly, the seaweed is washed with water and anhydrous ethanol for several times, dried in a vacuum drying oven at 60±5 ℃ for a certain time until the weight is constant, and the dried seaweed is ground into powder for standby use; Thirdly, the seaweed powder is put into a muffle furnace, the heating rate is 1-3 ℃ / min -1 , the temperature is raised to 300-500 ℃, and the temperature is kept for 1-3 h to obtain a pre-carbonized product; Fourthly, the product is mixed with potassium hydroxide at a mass ratio of 1:1-1:3, put into a tube furnace, and N2 is introduced, and the temperature is kept stable under the Ar gas flow, the heating rate is 1-3 ℃ / min -1to 800~1000 ℃, and keeping for 2 h to obtain an activated product; In the fourth step, the potassium hydroxide in the activated product is neutralized by dilute hydrochloric acid, and washed by distilled water until the pH is 7, and then dried in a vacuum drying box set at 60 ±5 ℃ for a constant weight to obtain the biomass-derived carbon material.

[0006] Further, the lead oxide powder has an oxidation degree of 69~74%, and a particle size of ≤6 μm.

[0007] Further, the hydroxyl cellulose has a viscosity grade of 400~800 mPa·s, and a particle size of ≤150 μm.

[0008] A preparation method of a lead paste for a negative electrode of a lead-carbon storage battery, comprising the following steps: S1, according to a certain proportion, humic acid, sodium lignosulfonate and biomass-derived carbon are mixed and dried to obtain a mixture A; S2, the mixture A and barium sulfate according to a certain proportion are added into a ball mill to mix to obtain a mixture B; S3, according to a certain proportion, hydroxyl cellulose is dissolved in deionized water to obtain a hydroxyl cellulose solution; S4, the mixture B and short fibers are dry mixed with lead powder in a paste mixer, and the hydroxyl cellulose solution, the remaining deionized water and sulfuric acid are added respectively for water mixing and acid mixing to obtain the negative lead paste.

[0009] Further, the stirring time in S1 is >20 min, and the mixture is dried after sufficient mixing at a drying temperature ≥60℃ for >6h.

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

[0011] Further, the dry mixing time in S4 is 6~12 min, and the hydroxyl cellulose solution, the remaining deionized water and sulfuric acid are respectively water mixed and acid mixed, the water adding time is 1~3 min, the water mixing time is 6~12 min, the density of the sulfuric acid is 1.4g / cm 3 , the acid adding time is 16~20 min, and the acid mixing time is 6~12 min.

[0012] Compared with the prior art, the present application has the following advantages: In view of the high cost of commercial carbon materials in lead-carbon batteries, a lead-carbon battery with cheap carbon material doped negative electrode material is proposed.

[0013] The present application can effectively reduce the cost of carbon materials in the additive, inhibit irreversible lead sulfate, improve the hydrogen evolution potential, and improve the stability of the additive. Among them, the biomass-derived carbon material has wide sources, low cost and simple preparation, and can be mass-produced. It has a rich porous structure, which helps to provide more reaction sites, speed up the electrolyte penetration and ion transmission speed, relieve the pressure difference in the plate, improve the utilization rate of active materials, etc. The biomass itself is rich in N, O and other elements, and the heteroatom doping after carbonization can effectively improve the hydrogen evolution potential of lead-acid batteries; the lignin carbon mixture prepared by mixing humic acid, sodium lignosulfonate and biomass-derived carbon in the additive ratio, then drying, is added to the negative electrode, so that the lignin carbon mixture is uniformly distributed in the internal and surface layers of the negative electrode, solving the problem of instability of sodium lignosulfonate, and having excellent effect on inhibiting hydrogen evolution of the negative electrode; further mixing mixture A and barium sulfate in a ball mill to obtain mixture B, ensuring that the ground mixture and paste can be uniformly distributed in the active material, so that the performance of the mixed component materials in the battery can be fully played, and under the joint action of other additives such as hydroxy cellulose and short fibers, the cost of the battery is reduced, and the stability and service life are improved. BRIEF DESCRIPTION OF DRAWINGS

[0014] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiments or the prior art description. Obviously, the drawings in the following description are only a part of the embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor on the basis of the provided drawings.

[0015] Fig. 1 SEM image of the biomass-derived carbon material prepared in the present application.

[0016] Fig. 2 Discharge schematic diagram of the present application and the comparative example at room temperature.

[0017] Fig. 3 Cycle life curve of the present application and the comparative example. DETAILED DESCRIPTION

[0018] The technical solutions in the embodiments of the present application will be described clearly and completely in the following with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, not all. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0019] Example 1 A lead carbon battery negative lead paste, comprising the following materials by weight: biomass-derived carbon material 0.2 parts, sulfuric acid 6 parts, deionized water 12 parts, short fibers 0.08 parts, humic acid 0.1 part, sodium lignosulfonate 0.4 parts, carboxymethyl cellulose 0.4 parts, barium sulfate 0.6 parts, and lead oxide powder 100 parts.

[0020] The preparation method of the biomass-derived carbon material comprises the following steps: first, preparing raw materials, including laver, deionized water, anhydrous ethanol, potassium hydroxide, hydrochloric acid, and inert gas; second, washing the laver with water and anhydrous ethanol multiple times, drying it in a vacuum drying box at 60 ℃ for 24 h until the weight is constant, and grinding the dried laver into powder for standby use; third, placing the laver powder into a muffle furnace, heating at a rate of 2 ℃ / min -1 to 400 ℃, and keeping the temperature for 1 h to obtain a pre-carbonized product; fourth, mixing the product with KOH at a mass ratio of 1:2, placing it into a tube furnace, and passing Ar into it, keeping it under a stable Ar gas flow, heating at a rate of 2 ℃ / min -1 to 800 ℃, and keeping the temperature for 2 h to obtain an activated product; fifth, neutralizing the KOH in the activated product with dilute hydrochloric acid, washing it with a large amount of distilled water until the pH is 7, and drying it in a vacuum drying box set at 60 ℃ for 24 h until the weight is constant to obtain the biomass-derived carbon material.

[0021] Specifically, the lead powder has an oxidation degree of 72%, a particle size of 3-4 μm, and the hydroxyl cellulose has a viscosity grade of 500-600 mPa·s and a particle size of ≤150 μm.

[0022] A preparation method of a lead carbon battery negative lead paste, comprising the following steps: S1, mixing humic acid 0.1 part, lignosulfonate sodium 0.4 part, and biomass-derived carbon material 0.2 part in a certain proportion, drying after fully mixing, drying temperature 90 ℃, drying time 24 h, to obtain mixture A; S2, adding barium sulfate 0.6 part in a certain proportion to the mixture A into a ball mill for mixing, ball mill speed 200 rpm, pre-mixing time 0.5 h, to obtain mixture B; S3, dissolving hydroxyl cellulose 0.4 part in 4 parts of deionized water to prepare a hydroxyl cellulose solution; S4, adding short fibers 0.08 part to the mixture B into a paste mixer for dry mixing, dry mixing time 8 min, then adding hydroxyl cellulose solution 1 part and remaining deionized water 8 parts, sulfuric acid 6 parts respectively for water mixing and acid mixing, water adding time 2 min, water mixing time 6 min, sulfuric acid density 1.4 g / cm 3 , acid adding time 18 min, acid mixing time 6 min, to obtain the negative lead paste.

[0023] Example 2 A lead carbon battery negative lead paste, comprising the following materials by weight: biomass-derived carbon material 0.4 parts, sulfuric acid 9 parts, deionized water 16 parts, short fibers 0.09 parts, humic acid 0.2 parts, sodium lignosulfonate 0.3 parts, carboxymethyl cellulose 0.6 parts, barium sulfate 0.8 parts, and lead oxide powder 100 parts.

[0024] The preparation method of the biomass-derived carbon material comprises the following steps: first, preparing raw materials, preparing laver, deionized water, anhydrous ethanol, potassium hydroxide, hydrochloric acid, and inert gas; second, washing the laver with water and anhydrous ethanol multiple times, drying it in a vacuum drying box at 60 ℃ for 24 h to a constant weight, and grinding the dried laver into powder for standby use; third, placing the laver powder into a muffle furnace, heating at a rate of 2 ℃ / min -1 to 400 ℃, and keeping it at this temperature for 1 h to obtain a pre-carbonized product; fourth, mixing the product with KOH at a mass ratio of 1:2, placing it into a tube furnace, and passing Ar into it, keeping it under a stable Ar gas flow, heating at a rate of 2 ℃ / min -1 to 900 ℃, and keeping it at this temperature for 2 h to obtain an activated product; fifth, neutralizing the KOH in the activated product with dilute hydrochloric acid, washing it with a large amount of distilled water until the pH is 7, and drying it in a vacuum drying box set at 60 ℃ for 24 h to a constant weight to obtain the biomass-derived carbon material.

[0025] Specifically, the lead powder has an oxidation degree of 72%, a particle size of 3-4 μm, and the hydroxyl cellulose has a viscosity grade of 500-600 mPa·s and a particle size of ≤150 μm.

[0026] A preparation method of a lead carbon battery negative lead paste, comprising the following steps: S1, according to the proportion, mixing humic acid 0.2 parts, sodium lignosulfonate 0.3 parts, and biomass-derived carbon material 0.4 parts, and drying after fully mixing, the drying temperature is 75 ℃, the time is 36 h, to obtain mixture A; S2, adding barium sulfate 0.8 parts according to the proportion into the ball mill to mix and grind, the rotation speed of the ball mill is 300 rpm, the premixing time is 1 h, to obtain mixture B; S3, dissolving hydroxyl cellulose 0.6 parts in 6 parts of deionized water to prepare a hydroxyl cellulose solution; S4, adding short fibers 0.09 parts into the paste mixer with lead powder for dry mixing, the dry mixing time is 6 min, then adding hydroxyl cellulose solution 1.5 parts and the remaining deionized water 10 parts, sulfuric acid 9 parts respectively for water mixing and acid mixing, the water adding time is 2 min, the water mixing time is 6 min, and the sulfuric acid density is 1.4 g / cm 3The acid adding time is 18 min, and the acid mixing time is 6 min, so that the negative lead paste is prepared.

[0027] Example 3 The lead-carbon battery negative lead paste comprises the following materials by weight: 0.6 parts of biomass-derived carbon material, 12 parts of sulfuric acid, 20 parts of deionized water, 0.1 part of short fiber, 0.3 part of humic acid, 0.2 part of sodium lignosulfonate, 0.8 part of carboxymethyl cellulose, 1 part of barium sulfate, and 100 parts of lead oxide powder.

[0028] The preparation method of the biomass-derived carbon material comprises the following steps: first, preparing raw materials, including laver, deionized water, anhydrous ethanol, potassium hydroxide, hydrochloric acid, and inert gas; second, washing the laver with water and anhydrous ethanol multiple times, drying the laver in a vacuum drying box at 60 ℃ for 24 h until the weight is constant, and grinding the dried laver into powder for standby; third, placing the laver powder into a muffle furnace, heating at a rate of 2 ℃ / min -1 to 400 ℃, and keeping the temperature for 1 h to obtain a pre-carbonized product; fourth, mixing the product with KOH at a mass ratio of 1:2, placing it into a tube furnace, and passing Ar to keep it under a stable Ar gas flow, heating at a rate of 2 ℃ / min -1 to 1000 ℃, and keeping the temperature for 2 h to obtain an activated product; fifth, neutralizing the KOH in the activated product with dilute hydrochloric acid, washing it with a large amount of distilled water until the pH is 7, and drying it in a vacuum drying box set at 60 ℃ for 24 h until the weight is constant to obtain the biomass-derived carbon material.

[0029] Specifically, the lead powder has an oxidation degree of 72%, a particle size of 3-4 μm, the lead powder has an oxidation degree of 72%, a particle size of 3-4 μm, the hydroxyl cellulose has a viscosity grade of 500-600 mPa·s, and a particle size of ≤150 μm.

[0030] A preparation method of a lead-carbon battery negative lead paste comprises the following steps: S1, according to the proportion, the humic acid 0.3 parts, the sodium lignosulfonate 0.2 parts and the biomass-derived carbon material 0.6 parts are fully mixed and then dried, the drying temperature is 70 ℃, the time is 40 h, and a mixture A is obtained; S2, the mixture A and the barium sulfate 1 part according to the proportion are added into a ball mill for mixing and grinding, the rotation speed of the ball mill is 400 rpm, the premixing time is 1.5 h, and a mixture B is obtained; S3, the carboxymethyl cellulose 0.8 parts is added into 8 parts of deionized water for dissolution, and a carboxymethyl cellulose solution is prepared; S4, add mixture B and short fiber 0.1 part into the paste mixer and dry mix with lead powder for 10 min, then add carboxymethyl cellulose solution 2 parts and remaining deionized water 12 parts, sulfuric acid 12 parts respectively for water mixing and acid mixing, water adding time 1 min, water mixing time 5 min, sulfuric acid density 1.4 g / cm 3 , acid adding time 18 min, acid mixing time 6 min, thereby obtaining the negative lead paste.

[0031] Comparative example A negative lead paste for lead-acid storage battery comprises the following materials by weight: acetylene black 0.4 parts, sulfuric acid 9 parts, deionized water 16 parts, short fiber 0.09 parts, humic acid 0.2 parts, sodium lignosulfonate 0.3 parts, carboxymethyl cellulose 0.6 parts, barium sulfate 0.8 parts, and lead oxide powder 100 parts.

[0032] A method for preparing a negative lead paste for lead-acid storage battery comprises adding acetylene black 0.4 parts, sulfuric acid 9 parts, deionized water 16 parts, short fiber 0.09 parts, humic acid 0.2 parts, sodium lignosulfonate 0.3 parts, carboxymethyl cellulose 0.6 parts, barium sulfate 0.8 parts, and lead oxide powder 100 parts into a paste mixer, dry mixing with lead powder for 6 min, water mixing and acid mixing with deionized water 16 parts and sulfuric acid 9 parts respectively, water adding time 2 min, water mixing time 6 min, sulfuric acid density 1.4 g / cm 3 , acid adding time 18 min, acid mixing time 6 min, thereby obtaining the negative lead paste.

[0033] The negative lead pastes of example 1, example 2, example 3 and the comparative example above are used to make negative plates, and it should be noted that the preparation process of the negative plates is the existing conventional process, which is not described in detail in this scheme. Under the condition that the plate ratio, separator and battery shell are completely the same, the acid filling is carried out to form the storage battery. The following test methods are used: 1. 10-hour rate capacity test: the fully charged storage battery is discharged within 1 h-24 h after the end of charging, and the discharge current is I 10 (A) Current discharge, the temperature around the storage battery is maintained at 20-25°C. The change of current value should not be greater than 1% within the discharge time, and when the single cell voltage of the storage battery reaches 1.80 V, the discharge is stopped and the discharge time is recorded, and the discharge capacity is calculated.

[0034] 2. Cycle life test: the temperature around the storage battery is maintained at 20-25°C, a) discharge the storage battery to the single cell voltage of 1.80 V at I 10 (A) Current discharge to the single cell voltage of 1.80 V; b) limit voltage 2.35 V / single, discharge at 2.5I 10 (A) Charge for 12 h; c) repeat steps a) and b) (when the discharge time of step a) is less than 8 hours, the life test is terminated).

[0035] As can be seen from the above, Figs. 1-3 The carbon material used in embodiments 1-3 of the present application has a developed porous structure and a large specific surface area, which can effectively increase the contact interface between the electrolyte and the active material, thereby improving the electrochemical reaction activity and the capacitance characteristics of the negative electrode material. The negative lead paste battery prepared using the carbon material has improved 10-hour rate capacity and significantly prolonged cycle life, and the residual capacity under the same cycle number is higher than that of the comparative examples. Further, the preparation cost of the biomass-derived carbon material is usually only 1 / 5-1 / 20 of that of the commercial carbon material, which has a significant economic advantage. Therefore, replacing part of the commercial carbon material with the biomass-derived carbon material can be used as a feasible optimization scheme for low-cost lead-carbon batteries.

[0036] The present application has simple components, low production cost, and the prepared negative plate has good cycle life and wide application.

[0037] The above examples are only used to help understand the method of the present application and its core idea. It should be noted that for those skilled in the art, without departing from the principles of the present application, the present application can be improved and modified in several ways, and these improvements and modifications also fall within the protection scope of the claims of the present application.

Claims

1. A lead paste for the negative electrode of a lead-carbon battery, characterized in that, Includes the following parts by weight of materials: The composition includes: 0.2-0.6 parts biomass-derived charcoal material, 6-12 parts sulfuric acid, 12-20 parts deionized water; 0.08-0.1 parts short fiber, 0.1-0.3 parts humic acid, 0.2-0.4 parts sodium lignosulfonate, 0.4-0.8 parts carboxymethyl cellulose, 0.6-1 parts barium sulfate, and 100 parts lead oxide powder.

2. The lead paste for the negative electrode of a lead-carbon battery according to claim 1, characterized in that, The method for preparing the biomass-derived char material includes the following steps: The first step is to prepare the raw materials, including seaweed, deionized water, anhydrous ethanol, potassium hydroxide, hydrochloric acid, and inert gas. The second step is to wash the laver with water and anhydrous ethanol several times, dry it in a vacuum drying oven at 60±5 ℃ for a set time until constant weight, and then grind the dried laver into powder for later use. The third step is to place the seaweed powder into a muffle furnace and heat it at a rate of 1-3 °C / min. -1 The temperature is increased to 300-500 ℃ and kept at that temperature for 1-3 h to obtain the pre-carbonized product. Fourth step: Mix the product with potassium hydroxide at a mass ratio of 1:1 to 1:3, place the mixture in a tube furnace, introduce N2, maintain a stable Ar gas flow, and raise the temperature at a rate of 1 to 3 °C / min. -1 Heat to 800~1000 ℃ and keep warm for 2 h to obtain the activated product; The fourth step involves neutralizing the potassium hydroxide in the activation product with dilute hydrochloric acid, washing it with distilled water until the pH reaches 7, and then drying it in a vacuum drying oven set at 60 ± 5 ℃ for a set time until constant weight is achieved, thus obtaining the biomass-derived carbon material.

3. The lead paste for the negative electrode of a lead-carbon battery according to claim 1 or 2, characterized in that, The lead oxide powder has an oxidation degree of 69-74% and a particle size of ≤6 μm.

4. The lead paste for the negative electrode of a lead-carbon battery according to claim 1 or 2, characterized in that, The hydroxycellulose has a viscosity grade of 400~800 mPa·s and a particle size of ≤150 μm.

5. A method for preparing lead paste for the negative electrode of a lead-carbon battery as described in any one of claims 1-4, characterized in that, Includes the following steps: S1. Humic acid, sodium lignosulfonate and biomass-derived char are mixed thoroughly in a certain proportion and then dried to obtain mixture A. S2. Mix mixture A with barium sulfate in a certain proportion in a ball mill to obtain mixture B; S3. Dissolve hydroxycellulose in deionized water according to the proportion to obtain a hydroxycellulose solution; S4. After mixing the mixture B with the short fibers and dry mixing with the lead powder in the paste mixing machine, the hydroxycellulose solution and the remaining deionized water and sulfuric acid are added to perform water mixing and acid mixing respectively, thereby obtaining the negative electrode lead paste.

6. The method for preparing lead paste for the negative electrode of a lead-carbon battery according to claim 5, characterized in that, The mixing time in S1 is >20 min. After thorough mixing, the mixture is dried at a temperature ≥60℃ for a time >6 h.

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

8. The method for preparing lead paste for the negative electrode of a lead-carbon battery according to claim 5 or 6, characterized in that, The dry mixing time in S4 is 6-12 min. It is then mixed with the hydroxycellulose solution and the remaining deionized water and sulfuric acid, respectively, with water addition taking 1-3 min and water mixing time taking 6-12 min. The sulfuric acid has a density of 1.4 g / cm³. 3 Add acid for 16-20 minutes and mix acid for 6-12 minutes.

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