A positive lead paste for lead-sodium storage batteries, a method for preparing the same, and a method for preparing a positive plate

Abstract

The application discloses a lead-sodium storage battery positive pole lead paste in the technical field of storage batteries, which comprises the following components by weight: lead oxide powder 100 parts, sulfuric acid 6-10 parts, deionized water 14-24 parts, short fibers 0.05-0.07 parts, lead dioxide 2-8 parts, lead sulfate 1-2 parts, calcium sulfate 0.5-1.5 parts, stannous sulfate 0.05-0.15 parts, antimony trioxide 0.05-0.15 parts, carbon black 0.5-1 part, sodium hydroxymethyl cellulose 0.1-0.2 parts and mixed carbon material 0.1-0.5 parts. Through the design improvement of the process, the application can effectively improve the formation efficiency, low-temperature performance and service life of the storage battery.

Description

TECHNICAL FIELD

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

[0002] The positive plate of lead-acid battery is the core component of lead-acid battery, and the performance of the positive plate will directly affect the capacity and service life of the battery. Optimizing the positive plate is the key to improving the performance of the battery. In the production process of the storage battery, how to reduce the formation capacity to control the production cost while ensuring the formation efficiency of the battery is a subject that has been tested.

[0003] The traditional positive lead paste formula is to dry mix, water mix and acid mix lead oxide powder, sulfuric acid, deionized water, short fibers and additives in a certain proportion to prepare lead paste, and then fill and coat the lead paste on the positive grid by a plate coating machine, and then acid is poured, the surface is dried, and the positive plate is prepared after solidification. Additives commonly used are red lead, graphite, etc. Red lead is added to the active material of the positive plate, which can significantly improve the conversion efficiency of the active material of the positive plate, but the impurities in the red lead are uncontrollable, and the battery often has poor uniformity and large self-discharge during use. Although graphite can enhance the conductivity of the plate, the effect of releasing capacity under low temperature conditions is not very obvious. The positive plate additive can also use lead dioxide (referring to the production of scrap positive plate active material), which can improve the formation efficiency, and the impurities produced are controllable, which can replace red lead. Calcium sulfate is beneficial to low temperature performance, and lead sulfate is beneficial to the cycle life of the plate, but it increases the difficulty of formation. How to solve the mutual restriction between additives to improve the formation efficiency, low temperature performance and service life of the storage battery, therefore, a lead-sodium storage battery positive lead paste, its preparation method and a positive plate preparation method are needed to solve the above problems. SUMMARY

[0004] In view of the deficiencies in the prior art, the present application provides a lead-sodium storage battery positive lead paste, its preparation method and a positive plate preparation method, which can effectively improve the formation efficiency, low temperature performance and service life of the storage battery.

[0005] The purpose of the present application is achieved by a lead-sodium storage battery positive lead paste, which comprises the following components by weight: lead oxide powder 100 parts, sulfuric acid 6-10 parts, deionized water 14-24 parts, short fiber 0.05-0.07 parts, lead dioxide 2-8 parts, lead sulfate 1-2 parts, calcium sulfate 0.5-1.5 parts, stannous sulfate 0.05-0.15 parts, antimony trioxide 0.05-0.15 parts, carbon black 0.5-1 parts, sodium hydroxymethyl cellulose 0.1-0.2 parts, and mixed carbon material 0.1-0.5 parts.

[0006] Further, the oxidation degree of the lead powder is 72-80%, and the particle size is ≤5 μm.

[0007] Further, the mixed carbon material includes graphite, acetylene black, graphene.

[0008] A preparation method of a positive lead paste of a lead-sodium storage battery, comprising the following steps:

[0009] Step 1, according to the proportion, according to the proportion, calcium sulfate, stannous sulfate, antimony trioxide are premixed to obtain mixture A;

[0010] Step 2, according to the proportion, lead dioxide, lead sulfate is added to the paste mixer and dry mixed with lead oxide powder;

[0011] Step 3, mixture A, short fibers and mixed carbon materials are added to the paste mixer and dry mixed with the product of step 2;

[0012] Step 4, deionized water and sulfuric acid are respectively added to the paste mixer for water mixing and acid mixing, thereby preparing the positive lead paste.

[0013] Further, the ball mill is used for premixing in step 1, the rotation speed of the ball mill is 200-300 rpm, and the premixing time is 0.5-1 h.

[0014] Further, the dry mixing time in step 2 is 1-5 min, and the dry mixing time in step 3 is 5-10 min.

[0015] Further, in step 4, deionized water and sulfuric acid are respectively added to the paste mixer for water mixing and acid mixing, the water adding 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 adding time is 15-20 min, and the acid mixing time is 5-10 min.

[0016] A preparation method of a positive plate of a lead-sodium storage battery, using the positive lead paste of the lead-sodium storage battery described above, comprising the following steps:

[0017] Step 1, preparing a carbon black aqueous solution, according to the following weight components: carbon black 0.5-1 part, deionized water 5-10 parts, thickening agent 0.1-0.2 parts;

[0018] Step 2, uniformly coating the positive lead paste on the positive alloy grid;

[0019] Step 3, spraying the carbon black aqueous solution on the surface of the lead paste, then performing acid washing, surface drying and curing treatment to obtain the positive plate.

[0020] Further, the sodium hydroxymethyl cellulose is a thickening agent; the amount of the carbon black aqueous solution is 10-30 mg per gram of lead paste for spraying on both sides, the acid washing density is 1.15 g / cm 3 , and the surface drying temperature is 120-140 DEG C.

[0021] Further, the curing and drying treatment process in step 3 is as follows:

[0022] Step a, relative humidity is 95~100%, temperature is 65~70℃, control time is 4~5h;

[0023] Step b, relative humidity is 85~90%, temperature is 70~76℃, control time is 6~8h;

[0024] Step c, relative humidity is 85~90%, temperature is 50~55℃, control time is 16~18h;

[0025] Step d, relative humidity is 5~20%, temperature is 75~80℃, control time is 30~32h.

[0026] Compared with the prior art, the beneficial effects of the present application are that: calcium sulfate, stannous sulfate and diantimony trioxide are premixed to obtain a mixture A, physical intercalation is realized, the powder particle size is uniform, it is ensured that the mixture after grinding and the paste can be uniformly distributed in the active substance, at the same time, the calcium sulfate particles become smaller, the influence on the formation efficiency is reduced, so as to play a role in the low temperature performance of the storage battery; the red lead is replaced by lead dioxide, the problem of the purity of red lead affecting the storage battery is solved, and the formation efficiency is improved; lead dioxide and tetrabasic lead sulfate are dry-mixed with lead oxide powder in priority, the uniformity of distribution is effectively realized; the carbon black aqueous solution is sprayed on the surface of the positive plate, which can effectively increase the initial conductivity of the plate, and the large current discharge performance at low temperature is more obvious. In summary, through the design and improvement of the process, the formation efficiency, low temperature performance and service life of the storage battery can be effectively improved. BRIEF DESCRIPTION OF DRAWINGS

[0027] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the drawings needed to be used in the embodiments or the prior art description will be briefly introduced below. Obviously, the drawings in the following description are only 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.

[0028] Fig. 1 The application is applied to the discharge schematic diagram of the storage battery under low temperature state.

[0029] Fig. 2 The application is applied to the discharge schematic diagram of the storage battery under normal temperature state.

[0030] Fig. 3 The application is applied to the cycle life curve diagram of the storage battery. DETAILED DESCRIPTION

[0031] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by a person of ordinary skill in the art without creative effort belong to the scope of protection of the present application.

[0032] Embodiment 1

[0033] A preparation method of a positive plate of a lead-sodium storage battery, comprising:

[0034] S1, preparing a positive lead paste.

[0035] The positive lead paste comprises 100 parts of lead oxide powder, 6 parts of sulfuric acid, 14 parts of deionized water, 0.05 parts of short fibers, 2 parts of lead dioxide, 1 part of lead sulfate, 0.5 parts of calcium sulfate, 0.05 parts of stannous sulfate, 0.05 parts of antimony trioxide, 0.5 parts of carbon black, 0.1 parts of sodium hydroxymethyl cellulose, and 0.1 parts of mixed carbon materials.

[0036] Specifically, the degree of oxidation of the lead oxide powder is 72%, and the particle size is 2-3 μm; and the mixed carbon materials are 0.05 parts of graphite, 0.025 parts of acetylene black, and 0.025 parts of graphene.

[0037] The step of preparing the positive lead paste is as follows:

[0038] S1-1, according to the above proportions, 0.5 parts of calcium sulfate, 0.05 parts of stannous sulfate, and 0.05 parts of antimony trioxide are pre-mixed by a ball mill, the rotation speed of the ball mill is 200 rpm, and the pre-mixing time is 1 h;

[0039] S1-2, according to the above proportions, 2 parts of lead dioxide and 1 part of lead sulfate are added to a paste mixer and dry-mixed with the lead oxide powder for 1 min;

[0040] S1-3, the product of S1-1, 0.05 parts of short fibers, and 0.1 parts of mixed carbon materials are added to the paste mixer and dry-mixed with the lead powder for 5 min;

[0041] S1-4, deionized water and sulfuric acid are respectively mixed with the paste in the paste mixer, the water mixing time is 1 min, the water mixing time is 5 min, the density of the sulfuric acid is 1.4 g / cm3, the acid adding time is 15 min, and the acid mixing time is 5 min, so as to obtain the positive lead paste.

[0042] S2, preparing a positive plate, the positive plate comprising the positive lead paste and a positive plate grid.

[0043] The step of preparing the positive plate is as follows:

[0044] Step 2-1, prepare a carbon black aqueous solution with the following weight components: carbon black 0.5 parts, deionized water 5 parts, thickening agent sodium hydroxymethyl cellulose 0.1 parts;

[0045] Step 2-2, evenly coat the prepared positive lead paste of S1 on the positive alloy grid;

[0046] Step 2-3, spray the carbon black aqueous solution on the surface of the lead paste, and then perform solidification treatment after acid washing and surface drying to obtain a positive plate. The amount of carbon black aqueous solution used is 10 mg per gram of lead paste, and the acid washing density is 1.15 g / cm3. The surface drying temperature is 120°C.

[0047] Specifically, the solidification and drying treatment process is as follows:

[0048] Step 1: relative humidity 95-100%, temperature 70°C, control time 4h;

[0049] Step 2: relative humidity 85-90%, temperature 76°C, control time 8h;

[0050] Step 3: relative humidity 85-90%, temperature 55°C, control time 18h;

[0051] Step 4: relative humidity 5-20%, temperature 80°C, control time 30h.

[0052] Example 2

[0053] A preparation method of a positive plate of a lead-sodium storage battery, comprising:

[0054] S1, preparing a positive lead paste.

[0055] The positive lead paste comprises 100 parts of lead oxide powder, 8 parts of sulfuric acid, 19 parts of deionized water, 0.06 parts of short fibers, 5 parts of lead dioxide, 1.5 parts of lead sulfate, 1 part of calcium sulfate, 0.1 parts of stannous sulfate, 0.1 parts of antimony trioxide, 0.75 parts of carbon black, 0.15 parts of sodium hydroxymethyl cellulose, and 0.3 parts of mixed carbon material.

[0056] Specifically, the lead oxide powder has an oxidation degree of 76% and a particle size of 3-4 μm, and the mixed carbon material comprises 0.2 parts of graphite, 0.05 parts of acetylene black, and 0.05 parts of graphene.

[0057] The preparation steps of the positive lead paste are as follows:

[0058] S1-1, according to the above proportions, the calcium sulfate 1 part, the stannous sulfate 0.1 part, and the antimony trioxide 0.1 part are pre-mixed by a ball mill at a speed of 250 rpm for 45 minutes;

[0059] S1-2, according to the above proportion, lead dioxide 5 parts, lead sulfate 1.5 parts are added into the paste mixer and dry mixed with lead oxide powder for 3 min;

[0060] S1-3, the product of S1-1 is added into the paste mixer with short fibers 0.06 parts, mixed carbon material 0.3 parts and lead powder for dry mixing for 7.5 min;

[0061] S1-4, water mixing and acid mixing are carried out in the paste mixer with deionized water and sulfuric acid respectively, water mixing time is 2 min, water mixing time is 7.5 min, sulfuric acid density is 1.4 g / cm3, acid mixing time is 17.5 min, acid mixing time is 7.5 min, thereby obtaining the positive lead paste.

[0062] S2, a positive plate is prepared, the positive plate comprises the positive lead paste and the positive plate grid.

[0063] The preparation of the positive plate is as follows:

[0064] Step 2-1, a carbon black aqueous solution is prepared according to the following weight components: carbon black 0.75 parts, deionized water 7.5 parts, thickening agent sodium hydroxymethyl cellulose 0.15 parts;

[0065] Step 2-2, the prepared positive lead paste of S1 is evenly coated on the positive alloy plate grid,

[0066] Step 2-3, the surface of the lead paste is sprayed with the carbon black aqueous solution, and after acid spraying, surface drying and curing treatment, the positive plate is prepared, the amount of the carbon black aqueous solution is 20 mg per gram of lead paste for spraying on both sides, the acid spraying density is 1.15 g / cm3, and the surface drying temperature is 130℃.

[0067] Specifically, the curing and drying treatment process is as follows:

[0068] Step 1, the relative humidity is 95-100%, the temperature is 67℃, and the control time is 4.5 h;

[0069] Step 2, the relative humidity is 85-90%, the temperature is 73℃, and the control time is 7 h;

[0070] Step 3, the relative humidity is 85-90%, the temperature is 53℃, and the control time is 17 h;

[0071] Step 4, the relative humidity is 5-20%, the temperature is 78℃, and the control time is 31 h.

[0072] Example 3

[0073] A preparation method of a positive plate of a lead-sodium storage battery comprises:

[0074] S1, a positive lead paste is prepared.

[0075] The positive lead paste comprises 100 parts of lead oxide powder, 10 parts of sulfuric acid, 24 parts of deionized water, 0.07 parts of short fibers, 8 parts of lead dioxide, 2 parts of lead sulfate, 1.5 parts of calcium sulfate, 0.15 parts of stannous sulfate, 0.15 parts of antimony trioxide, 1 part of carbon black, 0.2 parts of sodium hydroxymethyl cellulose, and 0.5 parts of mixed carbon material.

[0076] Specifically, the lead oxide powder has an oxidation degree of 80% and a particle size of 4-5 μm, and the mixed carbon material comprises 0.3 parts of graphite, 0.1 parts of acetylene black, and 0.1 parts of graphene.

[0077] The positive lead paste is prepared by the following steps:

[0078] S1-1, the calcium sulfate, the stannous sulfate and the antimony trioxide are premixed by a ball mill at a speed of 300 rpm for 0.5 h according to the above proportions;

[0079] S1-2, the lead dioxide and the lead sulfate are added into a paste mixer and dry-mixed with the lead oxide powder for 5 min according to the above proportions;

[0080] S1-3, the product of S1-1, the short fibers and the mixed carbon material are added into the paste mixer and dry-mixed with the lead powder for 10 min;

[0081] S1-4, the deionized water and the sulfuric acid are respectively mixed with the product in the paste mixer, the water is added for 3 min, the water mixing is performed for 10 min, the sulfuric acid is added for 20 min, and the acid mixing is performed for 10 min, so as to obtain the positive lead paste.

[0082] S2, a positive plate is prepared, which comprises the positive lead paste and a positive plate grid.

[0083] The positive plate is prepared by the following steps:

[0084] Step 2-1, a carbon black aqueous solution is prepared according to the following weight components: 1 part of carbon black, 10 parts of deionized water, and 0.2 parts of thickening agent sodium hydroxymethyl cellulose;

[0085] Step 2-2, the prepared positive lead paste of S1 is evenly coated on the positive alloy plate grid;

[0086] Step 2-3, the surface of the lead paste is sprayed with the carbon black aqueous solution, and then the lead paste is subjected to acid spraying, surface drying and curing treatment to obtain the positive plate, the amount of the carbon black aqueous solution is 20 mg per gram of the lead paste, the acid spraying density is 1.15 g / cm3, and the surface drying temperature is 140°C.

[0087] Specifically, the curing and drying treatment process is as follows:

[0088] Step 1, relative humidity is 95~100%, temperature is 65℃, control time length is 5h;

[0089] Step 2, relative humidity is 85~90%, temperature is 70℃, control time length is 6h;

[0090] Step 3, relative humidity is 85~90%, temperature is 50℃, control time length is 18h;

[0091] Step 4, relative humidity is 5~20%, temperature is 75℃, control time length is 32h.

[0092] Comparative Example

[0093] The positive lead paste comprises 100 parts of lead oxide powder, 8 parts of sulfuric acid, 12 parts of deionized water, 0.06 parts of short fiber, 0.1 parts of stannous sulfate, 0.1 parts of antimony trioxide and 0.3 parts of graphite. The oxidation degree of the lead powder is 76%, and the particle size is 3~4μm.

[0094] The preparation steps of the positive lead paste are as follows: according to the proportion, 0.06 parts of short fiber, 0.1 parts of stannous sulfate, 0.1 parts of antimony trioxide and 0.3 parts of graphite are added into the paste mixer and dry mixed with the lead powder for 7.5min; and the deionized water and sulfuric acid are respectively mixed with water and acid in the paste mixer, the water adding time is 2min, the water mixing time is 7.5min, the sulfuric acid density is 1.4g / cm3, the acid adding time is 17.5min, and the acid mixing time is 7.5min.

[0095] The preparation steps of the positive plate are as follows: the prepared positive lead paste is evenly coated on the positive alloy grid, and then the positive plate is prepared after acid spraying, surface drying and curing treatment. The acid spraying density is 1.15g / cm3, and the surface drying temperature is 130℃.

[0096] The curing and drying treatment process is as follows: step 1, relative humidity is 95~100%, temperature is 70℃, control time length is 4h; step 2, relative humidity is 85~90%, temperature is 50℃, control time length is 30h; step 3, relative humidity is 5~20%, temperature is 75℃, control time length is 30h.

[0097] The positive plates of example 1, example 2 and example 3 are used to make batteries in the same way as the comparative example, i.e. using the same plate ratio, separator and battery shell.

[0098] Lead dioxide content test method: after the internal formation of the battery is completed, dissection is performed, and the lead dioxide content is determined according to 6.4.1 of GB / T 23636-2017.

[0099] 10 hours rate capacity test: the fully charged battery is discharged with I10(A) current within 1h-24h after the end of charging, and the temperature around the battery is kept between 20-25℃. The change of current value should be no more than 1% within the discharge time, when the battery single voltage reaches 1.80V, stop discharging and record the discharge time, calculate the discharge capacity.

[0100] -40℃ low temperature capacity test: the fully charged battery is placed in-40℃±2℃ environment for 20h, and the battery is discharged with I10(A) current. During the discharge process, the temperature around the battery is kept between-40℃±2℃, the change of current value should be no more than 1%, when the battery single voltage reaches 1.80V, stop discharging and record the discharge time, calculate the discharge capacity.

[0101] Cycle life test: the temperature around the battery is kept between 20-25℃, a) discharge with I10(A) current to the battery single voltage reaches 1.80V; b) limit voltage 2.35V / single, charge with 2.5I10(A) for 12h; c) repeat a), b) steps. (When the discharge time of step a is less than 8 hours, the life test is terminated).

[0102]

[0103] From the above, it can be seen that, as shown in Table 1, the content of lead dioxide in the positive plate does not cause the problem of poor formation due to the addition of calcium sulfate, and the same effect as the comparative example is achieved, and the low temperature performance and cycle life are better. The components of the application are simple, the production cost is low, the performance of the prepared positive plate has good low temperature resistance and cycle life, and the application range is wide. Figs. 1-3

[0104] The above description of the embodiments is only used to help understand the method of the application and its core idea. It should be pointed out that for ordinary skilled in the art, without departing from the principles of the application, the 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 application.​

Claims

1. A method of manufacturing positive plates for lead-sodium storage batteries, characterized in that, It comprises the following steps: Step 1, prepare a carbon black aqueous solution, with the following weight components: carbon black 0.5-1 part, deionized water 5-10 parts, sodium hydroxymethyl cellulose 0.1-0.2 parts; Step 2, uniformly coat the positive lead paste on the positive alloy grid; the positive lead paste comprises the following weight components: lead oxide powder 100 parts, sulfuric acid 6-10 parts, deionized water 14-24 parts, short fibers 0.05-0.07 parts, lead dioxide 2-8 parts, lead sulfate 1-2 parts, calcium sulfate 0.5-1.5 parts, stannous sulfate 0.05-0.15 parts, antimony trioxide 0.05-0.15 parts, carbon black 0.5-1 parts, sodium hydroxymethyl cellulose 0.1-0.2 parts, and mixed carbon material 0.1-0.5 parts; the lead powder has an oxidation degree of 72-80% and a particle size of ≤5 μm; the mixed carbon material comprises graphite, acetylene black, and graphene; Step 3, spray the carbon black aqueous solution on the surface of the lead paste, and then perform acid leaching, surface drying, and curing treatment to obtain the positive plate.

2. The method of claim 1, wherein the positive plate of the lead-sodium battery is prepared by the steps of: The sodium hydroxymethyl cellulose is a thickening agent; the aqueous solution of carbon black is sprayed on both sides in an amount of 10-30 mg per gram of lead paste, and the acid density is 1.15 g / cm 3 , and the surface drying temperature is 120-140℃.

3. The method according to claim 1 or 2, characterized in that, The curing and drying treatment process in step 3 is as follows: Step a, relative humidity 95-100%, temperature 65-70℃, control time 4-5h; Step b, relative humidity 85-90%, temperature 70-76℃, control time 6-8h; Step c, relative humidity 85-90%, temperature 50-55℃, control time 16-18h; Step d, relative humidity 5-20%, temperature 75-80℃, control time 30-32h.

4. A method of producing a positive lead paste for a lead-sodium storage battery according to the method of producing a positive plate for a lead-sodium storage battery as claimed in any one of claims 1 to 3, characterized by, It comprises the following steps: Step 1, according to the proportion, pre-mix calcium sulfate, stannous sulfate, and antimony trioxide to obtain mixture A; Step 2, according to the proportion, add lead dioxide and lead sulfate to the paste mixer and dry-mix with the lead oxide powder; Step 3, add mixture A, short fibers, and mixed carbon material to the paste mixer and dry-mix with the product of step 2 according to the proportion; Step 4, add deionized water and sulfuric acid to the paste mixer respectively for water mixing and acid mixing, thereby obtaining the positive lead paste.

5. The method for preparing the positive electrode lead paste for a lead-sodium battery according to claim 4, characterized in that, In step 1, a ball mill is used for pre-mixing, with a rotation speed of 200-300 rpm and a pre-mixing time of 0.5-1h.

6. The method for producing positive lead paste for lead-sodium accumulators according to claim 4 or 5, characterized in that, In step 2, the dry-mixing time is 1-5 min, and in step 3, the dry-mixing time is 5-10 min.

7. The method of producing positive lead paste for lead-sodium batteries according to claim 4 or 5, characterized in that, In step 4, water mixing and acid mixing are respectively carried out with deionized water and sulfuric acid in the paste mixer, the water mixing 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 adding time is 15-20 min, and the acid mixing time is 5-10 min.

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