CN112670455B - Positive plate of lead storage battery and lead storage battery - Google Patents
Positive plate of lead storage battery and lead storage battery Download PDFInfo
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- CN112670455B CN112670455B CN202011564325.4A CN202011564325A CN112670455B CN 112670455 B CN112670455 B CN 112670455B CN 202011564325 A CN202011564325 A CN 202011564325A CN 112670455 B CN112670455 B CN 112670455B
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a positive plate of a lead storage battery and the lead storage battery. The positive plate of the lead storage battery comprises a positive plate grid and positive lead plaster coated on the positive plate grid, wherein the positive plate grid is subjected to oxide layer removing pretreatment, and velvet lead is generated on the surface of the plate grid; the positive lead plaster comprises an inner layer lead plaster coated on a grid, middle layer lead plasters coated on two sides of the inner layer lead plaster and outer layer lead plasters coated on the outer sides of the middle layer lead plasters on two sides, wherein the coating mass ratios of the inner layer lead plaster, the middle layer lead plaster and the outer layer lead plasters are respectively 10-20%, 45-60% and 25-45%. The positive lead plaster coated on the positive plate grid of the lead storage battery has different porosity, the porosity of the inner lead plaster is 45.2-48.3%, the porosity of the middle lead plaster is 40.6-43.2%, and the porosity of the outer lead plaster is 38.0-41.6%.
Description
Technical Field
The invention relates to the technical field of secondary batteries, in particular to a positive plate of a lead storage battery and the lead storage battery.
Background
A lead accumulator is an accumulator whose electrodes are made up mainly of lead and its oxide layer and whose electrolyte is sulfuric acid solution. The positive electrode active material of the lead storage battery is lead dioxide, the negative electrode active material is spongy metallic lead, and the electrolyte is sulfuric acid. When the lead-acid battery discharges, the active substances on the positive electrode and the negative electrode are simultaneously converted into lead sulfate. During charging, the lead sulfate on the positive electrode is oxidized into lead dioxide, and the lead sulfate on the negative electrode is reduced into spongy metallic lead. Sulfuric acid functions to conduct current and participates in the battery reaction.
Research has shown that the fundamental purpose of preparing lead paste for lead storage batteries is to produce lead paste particles having a certain shape and composition. The particles are basic constituent elements of the lead plaster, the lead plaster particles are mutually cross-linked to form a porous substance through filling a grid and curing a polar plate, and the porous substance is converted into an active substance through a chemical method through formation to form the polar plate of the lead storage battery. The structure of the basic lead sulfate, especially the lead dioxide active substance in the lead plaster influences the generated active substance, so that the stable positive lead plaster substance composition is the basis for ensuring enough porosity and stable structure of the pole plate, and the preparation of the lead plaster determines the capacity and energy parameters of the battery and the service life of the battery.
Patent document CN106910872B discloses a positive plate of a lead storage battery and the lead storage battery, wherein a lead paste raw material of the positive plate comprises lead powder, an additive, water and sulfuric acid, the additive comprises antimony trioxide and stannous sulfate, the preparation of the lead paste is completed in two parts, the additive of the first part comprises antimony trioxide and stannous sulfate, the reaction temperature is controlled to be not more than 50 ℃, the first lead paste containing 3BS is prepared, the second part does not comprise the above two additives, the reaction temperature is controlled to be 80-85 ℃, the second lead paste containing 4BS is prepared, and then physical mixing is performed, so that the positive lead paste contains effective amounts of 3BS and 4BS simultaneously, and the performances of the battery in the aspects of initial capacity and battery life are improved simultaneously. The method adopts a medium-temperature lead plaster mixing and curing process, avoids the conversion of 4BS and the further increase of the particle size, effectively controls the particle size and the content of 4BS in the lead plaster, and ensures the consistency of the battery.
Patent document CN109273716A discloses a long-life lead storage battery and a preparation method thereof, wherein a lead paste of a positive plate is completed by two parts, a first lead paste containing stannous sulfate, antimony trioxide and 3BS and a second lead paste containing 4BS are respectively prepared, then a sandwich type paste coating operation is performed, the first lead paste is coated on the inner layer, and the second lead paste is coated on the surface layer, so as to obtain a green plate; preparing a positive plate after medium-temperature curing, performing internal formation after assembling the battery, and initially charging by adopting higher current density to prepare the long-life lead storage battery. The method adopts sandwich paste coating to make the surface layer of the green plate have high content of 4BS, relieves the sulfation speed of the surface layer, and improves the alpha-PbO of the surface layer by combining with a large current formation process 2 The softening speed of the surface layer of the polar plate is reduced in the battery circulation process, and the cycle life of the battery is prolonged.
Patent document CN103762358B discloses a positive lead plaster for lead storage battery and a preparation method thereof, wherein the positive lead plaster comprises the following raw materials by mass percent: 7-10% of sulfuric acid with the concentration of 1.4g/mL, 8-12% of deionized water, 5-20% of red lead, 0.1-0.4% of colloidal graphite, 0.1-0.3% of stannous sulfate, 0.1-0.4% of anhydrous sodium sulfate, 0.2-0.5% of 4BS, 0.1-0.3% of antimony trioxide, 0.05-0.2% of polyester staple fiber and the balance of lead powder. After the storage battery is prepared from the lead plaster prepared by the formula and the preparation method, the storage battery has the characteristics of high initial capacity, long cycle life, good low-temperature performance and charging receiving capacity and the like.
The three schemes all disclose the method for manufacturing the lead storage battery pole plate by adopting two different lead pastes, which can improve the softening phenomenon of the active substance of the positive plate and prolong the cycle life of the battery, but does not improve the utilization rate of the active substance and the specific energy of the battery.
Disclosure of Invention
The invention discloses a positive plate of a lead storage battery and the lead storage battery, which solve the problems of low utilization rate of active substances of the positive plate and low specific energy in the conventional manufacturing process of the positive plate of the lead storage battery.
A positive plate of a lead storage battery comprises a positive plate grid and positive diachylon coated on the positive plate grid, wherein the positive diachylon comprises inner diachylon coated on the positive plate grid, middle diachylon coated on two sides of the inner diachylon and outer diachylon coated on the outer sides of the middle diachylon at two sides,
the inner lead plaster comprises the following components in percentage by mass: 22.7-28.6% of 1BS, 42.7-44.2% of 3BS, 2.8-4.0% of alpha-PbO, 14.1-22.0% of beta-PbO and 8.6-9.2% of Pb;
the middle lead plaster comprises the following components in percentage by mass: 57.3-67.2% of 3BS, 22.7-30.2% of alpha-PbO, 1.2-3.4% of beta-PbO and 8.2-9.1% of Pb;
the outer lead plaster comprises the following components in percentage by mass: 3.2-9.3% of 3BS, 2.0-3.7% of alpha-PbO, 11.3-21.9% of beta-PbO, 56.2-73.7% of 4BS and 8.6-9.2% of Pb.
Preferably, the coating mass of the inner layer lead plaster, the middle layer lead plaster and the outer layer lead plaster accounts for 10-20%, 45-60% and 25-45% of the total mass of the lead plaster.
Preferably, the porosity of the inner lead plaster is 45.2-48.3%, the porosity of the middle lead plaster is 40.6-43.2%, and the porosity of the outer lead plaster is 38.0-41.6%.
According to the total mass percentage of the inner lead plaster, 79.81-83.13% of lead powder, 0.08% of polyester staple fiber and 0.16% of antimony trioxide or stannous sulfate are dry-mixed and stirred for 5 minutes, 7.98-8.31% of water is added at room temperature for wet mixing for 10 minutes, 8.31-11.97% of sulfuric acid with the density of 1.4g/mL is added for stirring and reacting for 15 minutes, the reaction temperature is controlled to be not higher than 55 ℃, and the inner lead plaster with the apparent specific gravity of 4.5g/mL is obtained.
According to the total mass percentage of the middle-layer lead plaster, 84.53-87.49% of lead powder, 0.09% of polyester staple fiber and 0.17% of antimony trioxide or stannous sulfate are dry-mixed and stirred for 5 minutes, 8.45-8.75% of water is added at room temperature for wet mixing for 10 minutes, 3.50-6.76% of sulfuric acid with the density of 1.4g/mL is added for stirring and reacting for 15 minutes, the reaction temperature is controlled to be not higher than 65 ℃, and the middle-layer lead plaster with the apparent specific gravity of 4.5g/mL is obtained.
According to the total mass percentage of the outer layer lead plaster, 85.69-88.73% of lead powder, 0.09% of polyester staple fiber, 0.17% of colloidal graphite, 0.17-0.18% of red lead and 0.17-0.18% of 4BS seed crystal are dry-mixed and stirred for 5 minutes, then 8.57-8.87% of hot water with the temperature of 90 ℃ is added for wet mixing for 10 minutes under the condition of heat preservation, finally 1.78-5.14% of sulfuric acid with the density of 1.4g/mL is added for stirring and reacting for 15-30 minutes, the reaction temperature is controlled to be not lower than 85 ℃, and the outer layer lead plaster with the apparent specific gravity of 4.5g/mL is obtained.
The method comprises the steps of pretreating the oxidation-removed layer of a positive plate grid, namely, firstly, taking one positive plate grid as a positive electrode, connecting 5-20 positive plate grids in parallel as a negative electrode, and placing the positive plate grid and the negative electrode in sulfuric acid solution with the density of 1.05-1.15 g/mLCharging the positive plate grids for 0.5-5 hours in a sulfuric acid tank, wherein the current density of each positive plate grid connected in parallel is 0.1-0.5A/m 2 And velvet lead is generated on the surfaces of the parallel positive grids.
The invention also provides a lead storage battery, which comprises the positive plate of the lead storage battery.
Compared with the prior art, the invention has the following beneficial effects:
the positive plate of the battery is provided with the inner lead plaster layer, the middle lead plaster layer and the outer lead plaster layer from inside to outside in sequence, and the structure is stable. The porosity of the inner lead plaster is 45.2-48.3%, the porosity of the middle lead plaster is 40.6-43.2%, the porosity of the outer lead plaster is 38.0-41.6%, and after a sulfuric acid solution permeates into the inner layer from the outer layer, the reaction area between the sulfuric acid solution and the internal active substances is increased, so that the improvement of the conversion rate of the middle part of the pole plate and the internal active substances is facilitated. The pole plate is pretreated, velvet lead is generated on the surface of the pole plate, the reaction between the inner lead paste layer and the positive plate grid is facilitated, and a good corrosion layer is formed on the surface of the positive plate grid, so that the strength of the pole plate is improved, and the service life of a battery is prolonged.
Drawings
FIG. 1 is a microstructure diagram of the surface of a positive grid after pretreatment in example 1;
FIG. 2 is a microstructure view of an inner layer lead paste in example 1;
FIG. 3 is a microstructure view of a middle layer lead paste in example 1;
FIG. 4 is a microstructure view of an outer lead paste in example 1.
Detailed Description
1. Pretreatment of positive plate grid
Taking 6-DZF-20 positive grid, 1 as positive electrode, 5 parallel-connected positive electrodes, placing in a sulfuric acid tank containing sulfuric acid solution with density of 1.05g/mL, charging with 2.7A current for 5 hours, and controlling current density of each parallel-connected positive grid to be 0.5A/m 2 And velvet lead is generated on the surfaces of the parallel positive grids. After the energization, the positive grid as the negative electrode is placed in water for storage.
2. Preparation of inner lead plaster
According to the total mass of the inner lead plaster, 79.81% of lead powder, 0.08% of polyester staple fiber and 0.17% of antimony trioxide are dry-mixed and stirred for 5 minutes, 7.97% of water is added at room temperature for wet mixing for 10 minutes, 11.97% of sulfuric acid with the density of 1.4g/mL is added for stirring and reacting for 15 minutes, the reaction temperature is controlled to be not higher than 55 ℃, and the inner lead plaster with the apparent specific gravity of 4.5g/mL is obtained.
3. Preparation of middle lead plaster
According to the total mass of the middle-layer lead plaster, 84.53% of lead powder, 0.09% of polyester staple fiber and 0.17% of stannous sulfate are dry-mixed and stirred for 5 minutes, 8.45% of water is wet-mixed for 10 minutes at room temperature, 6.76% of sulfuric acid with the density of 1.4g/mL is added, and stirring reaction is carried out for 15 minutes, the reaction temperature is controlled to be not higher than 65 ℃, and the middle-layer lead plaster with the apparent specific gravity of 4.50g/mL is obtained.
4. Preparation of outer lead plaster
According to the total mass of the outer lead plaster, 85.69% of lead powder, 0.09% of polyester staple fiber, 0.17% of colloidal graphite, 0.17% of red lead and 0.17% of 4BS seed crystal are dry-mixed and stirred for 5 minutes, then 8.57% of hot water with the temperature of 90 ℃ is added under the condition of heat preservation for wet mixing for 10 minutes, finally 5.14% of sulfuric acid with the density of 1.4g/mL is added for stirring and reacting for 30 minutes, the reaction temperature is controlled to be not lower than 85 ℃, and the outer lead plaster with the apparent specific gravity of 4.5g/mL is obtained.
5. Positive plate and battery fabrication
Taking out the 6-DZF-20 positive grid stored in water after pretreatment, coating inner lead plaster firstly, then coating middle lead plaster and outer lead plaster on one surface of the positive grid in sequence, turning the pole piece to the other surface, and coating the middle lead plaster and the outer lead plaster in sequence. Wherein, the coating quality of inlayer lead plaster is 33.0g, and the total coating quality (including the total quality of two sides coating, the same below) of middle level lead plaster is 148.6g, and the total coating quality of outer lead plaster is 148.6g, and inlayer lead plaster volume, middle level lead plaster volume and outer lead plaster volume account for respectively positive pole lead plaster total mass to account for the ratio respectively: 10%, 45% and 45%. After coating, the raw positive plate is manufactured through surface acid spraying, surface drying, curing, drying and slitting. The green positive plate was taken for continuous drop test strength (results are shown in table 2). The positive plate, the negative plate and the separator are assembled into a semi-finished battery, and the semi-finished battery is formed into an experimental battery 1.
The microstructure of the pretreated positive grid (see results in fig. 1), the microstructure of the inner lead paste (see results in fig. 2), the microstructure of the middle lead paste (see results in fig. 3) and the microstructure of the outer lead paste (see results in fig. 4), and the porosity and composition (see table 1) of 3 lead pastes, the 2HR capacity of the battery, the composition of the plate after completion of discharge and the 100% DoD cycle life (see table 2) were tested.
Comparative example 1
1. Positive plate and battery fabrication
The inner lead plaster in the embodiment 1 is coated on the pretreated 6-DZF-20 positive grid, and the coating amount is 330 g. After the coating is finished, the raw positive plate is manufactured through surface acid spraying, surface drying, curing, drying and slitting. The green positive plate was taken and tested for drop strength (results are shown in table 2). And assembling the positive plate, the negative plate and the partition plate into a semi-finished battery, and forming the semi-finished battery into the comparative battery 1.
The 2HR capacity, plate composition after discharge and 100% DoD cycle life of the cell (results are shown in table 2).
Comparative example 2
1. Positive plate and battery fabrication
The middle lead plaster in example 1 was coated on the pretreated 6-DZF-20 positive grid in an amount of 330 g. After the coating is finished, the raw positive plate is manufactured through surface acid spraying, surface drying, curing, drying and slitting. The green positive plates were taken and tested for drop strength (results are shown in table 2). The positive plate, the negative plate and the separator are assembled into a semi-finished battery, and the comparative battery 2 is manufactured through the procedures of formation and the like.
The 2HR capacity, plate composition after discharge and 100% DoD cycle life of the cell (results are shown in table 2).
Comparative example 3
1. Positive plate and battery fabrication
The outer lead plaster in example 1 was coated on the pretreated 6-DZF-20 positive grid in an amount of 330 g. After coating, the raw positive plate is manufactured through surface acid spraying, surface drying, curing, drying and slitting. The green positive plate was taken and tested for drop strength (results are shown in table 2). And assembling the positive plate, the negative plate and the partition plate into a semi-finished battery, and forming the semi-finished battery into a comparative battery 3.
The 2HR capacity, plate composition after discharge and 100% DoD cycle life of the cell (results are shown in table 2).
Comparative example 4
1. Positive plate and battery fabrication
According to the scheme disclosed by patent document CN109273716A, the middle layer lead paste in example 1 is coated on the pretreated 6-DZF-20 positive grid, the coating amount is 220g, then the outer layer lead paste in example 1 is respectively coated on two sides of the middle layer lead paste, the coating amount of each side is 55g, and the mass ratio of the middle layer lead paste amount to the total amount of the outer layer lead paste coated twice is 2: 1. After coating, the raw positive plate is manufactured through surface acid spraying, surface drying, curing, drying and slitting. The green positive plates were taken and tested for drop strength (results are shown in table 2). And assembling the positive plate, the negative plate and the partition plate into a semi-finished battery, and forming the semi-finished battery into a comparative battery 4.
The 2HR capacity, plate composition after discharge and 100% DoD cycle life of the cell (results are shown in table 2).
Table 1 lead paste porosity and composition test results in example 1
TABLE 2 Pole plate and Battery test data
As can be seen from table 1, the porosity of the inner lead paste is the highest, the porosity of the middle lead paste is the second, the porosity of the outer lead paste is the lowest, and the contact areas from the outer layer to the inner plate, which are reacted with sulfuric acid, increase in sequence.
As can be seen from table 2, the positive plate manufactured in example 1 has the least amount of active material lost in the plate drop test, and the strength far exceeds that of the positive plate of the comparative example, showing that the binding force between the pretreated grid and the active material of the positive plate is stronger; the 2HR capacity and the positive plate active material utilization rate of the battery 1 in the example are respectively 2.1%, 15.2%, 20.4% and 16.3% higher than those of the battery in comparative examples 1 to 4, so that the positive plate active material utilization rate and the active material conversion rate are greatly improved; the battery life of example 1 was 61.7%, 13.4%, 0.7% and 6.6% higher than those of comparative examples 1 to 4, respectively, and the life performance of the experimental battery of example 1 was not inferior to that of the comparative battery.
Example 2
1. Pretreatment of positive plate grid
Taking 6-DZF-20 positive grid, 1 as positive electrode, 20 parallel-connected positive electrodes, placing in sulfuric acid tank containing sulfuric acid solution with density of 1.15g/mL, charging with 2.2A current for 0.5 hr, and passing through each parallel-connected positive grid with current density of 0.1A/m 2 And velvet lead is generated on the surfaces of the parallel positive grids. After the energization is finished, the positive plate grid as the negative electrode is placed in water for storage.
2. Preparation of inner lead plaster
According to the total mass of the inner lead plaster, 83.13 percent of lead powder, 0.08 percent of polyester staple fiber and 0.17 percent of stannous sulfate are dry-mixed and stirred for 5 minutes, 8.31 percent of water is added at room temperature for wet mixing for 10 minutes, 8.31 percent of sulfuric acid with the density of 1.4g/mL is added for stirring and reacting for 15 minutes, the reaction temperature is controlled to be not higher than 55 ℃, and the inner lead plaster with the apparent specific gravity of 4.5g/mL is obtained.
3. Preparation of middle lead plaster
According to the total mass of the middle-layer lead plaster, 87.49 percent of lead powder, 0.09 percent of polyester staple fiber and 0.17 percent of antimony trioxide are mixed and stirred for 5 minutes in a dry mode, 8.75 percent of water is mixed for 10 minutes in a wet mode at room temperature, 3.5 percent of sulfuric acid with the density of 1.4g/mL is added, the mixture is stirred and reacted for 15 minutes, the reaction temperature is controlled to be not higher than 65 ℃, and the middle-layer lead plaster with the apparent specific gravity of 4.5g/mL is obtained.
4. Preparation of outer lead plaster
According to the total mass of the outer-layer lead plaster, 88.73% of lead powder, 0.09% of polyester staple fiber, 0.17% of colloidal graphite, 0.18% of red lead and 0.18% of 4BS seed crystal are dry-mixed and stirred for 5 minutes, then 8.87% of hot water with the temperature of 90 ℃ is added under the condition of heat preservation for wet mixing for 10 minutes, finally 1.78% of sulfuric acid with the density of 1.4g/mL is added for stirring and reacting for 15 minutes, the reaction temperature is controlled to be not lower than 85 ℃, and the outer-layer lead plaster with the apparent specific gravity of 4.5g/mL is obtained.
5. Positive plate and battery fabrication
Taking out the 6-DZF-20 positive grid stored in water after pretreatment, coating inner lead plaster firstly, then coating middle lead plaster and outer lead plaster on one surface of the positive grid in sequence, turning the pole piece to the other surface, and coating the middle lead plaster and the outer lead plaster in sequence. The coating quality of the inner lead plaster is 49.5g, the total coating quality of the middle lead plaster (including the total quality of two-sided coating, the same below) is 198g, the total coating quality of the outer lead plaster is 82.6g, and the inner lead plaster amount, the middle lead plaster amount and the outer lead plaster amount respectively account for the total mass of the anode lead plaster in the ratio that: 15%, 60% and 25%. After the coating is finished, the raw positive plate is manufactured through surface acid spraying, surface drying, curing, drying and slitting. The green positive plate was taken for continuous drop test strength (results are shown in table 4). The positive plate, the negative plate and the separator are assembled into a semi-finished battery, and the semi-finished battery is formed into an experimental battery 2.
The porosity and composition of 3 lead pastes were tested (results are shown in table 3), the 2HR capacity of the cell, the composition of the plate after discharge and 100% DoD cycle life (results are shown in table 4).
Comparative example 5
1. Positive plate and battery fabrication
The inner lead plaster in example 2 was coated on the pretreated 6-DZF-20 positive grid in an amount of 330 g. After the coating is finished, the raw positive plate is manufactured through surface acid spraying, surface drying, curing, drying and slitting. The green positive plate was taken and tested for drop strength (results are shown in table 4). And assembling the positive plate, the negative plate and the partition plate into a semi-finished battery, and forming the semi-finished battery into a comparative battery 5.
The 2HR capacity, plate composition after discharge and 100% DoD cycle life of the cell (results are shown in table 4).
Comparative example 6
1. Positive plate and battery fabrication
The middle lead plaster in example 2 was coated on the pretreated 6-DZF-20 positive grid in an amount of 330 g. After coating, the raw positive plate is manufactured through surface acid spraying, surface drying, curing, drying and slitting. The green positive plate was taken and tested for drop strength (results are shown in table 4). The positive plate, the negative plate and the separator are assembled into a semi-finished battery, and the comparative battery 6 is manufactured through the procedures of formation and the like.
The 2HR capacity, plate composition after discharge and 100% DoD cycle life of the cell (results are shown in table 4).
Comparative example 7
1. Positive plate and battery fabrication
The outer lead plaster in example 2 was coated on the pretreated 6-DZF-20 positive grid in an amount of 330 g. After the coating is finished, the raw positive plate is manufactured through surface acid spraying, surface drying, curing, drying and slitting. The green positive plates were taken and tested for drop strength (results are shown in table 4). The positive plate, the negative plate and the separator are assembled into a semi-finished battery, and the comparative battery 7 is manufactured through the procedures of formation and the like.
The 2HR capacity, plate composition after discharge and 100% DoD cycle life of the cell (results are shown in table 4).
Comparative example 8
1. Positive plate and battery fabrication
According to the scheme disclosed by patent document CN109273716A, the middle-layer lead plaster in the example 2 is coated on the pretreated 6-DZF-20 positive grid, the coating amount is 220g, then the outer-layer lead plaster in the example 2 is respectively coated on two sides of the middle-layer lead plaster, the coating amount of each side is 55g, and the mass ratio of the middle-layer lead plaster amount to the total amount of the outer-layer lead plaster coated twice is 2: 1. After coating, the raw positive plate is manufactured through surface acid spraying, surface drying, curing, drying and slitting. The green positive plates were taken and tested for drop strength (results are shown in table 4). And assembling the positive plate, the negative plate and the partition plate into a semi-finished battery, and forming the semi-finished battery into a comparative battery 8.
The 2HR capacity, plate composition after discharge and 100% DoD cycle life of the cell (results are shown in table 4).
Table 3 lead paste porosity and composition test results in example 2
TABLE 4 Pole plate and Battery test data
As can be seen from table 3, the porosity of the inner lead paste is the highest, the porosity of the middle lead paste is the second, the porosity of the outer lead paste is the lowest, and the contact areas from the outer layer to the inner plate, which react with sulfuric acid, increase in sequence.
As can be seen from table 4, the positive plate manufactured in example 2 has the least amount of active material loss in the plate drop test, and the strength is far higher than that of the comparative positive plate, which shows that the binding force between the pretreated grid and the active material of the positive plate is stronger; the 2HR capacity and the positive plate active material utilization rate of the battery 2 in the example are respectively 5.3%, 14.4%, 18.3% and 17.7% higher than those of comparative examples 5 to 8, and the positive plate active material utilization rate and the active material conversion rate are greatly improved; the battery life of example battery 2 was 98.1%, 10.9%, 2.3%, and 4.9% higher than that of comparative examples 5 to 8, respectively, and the life performance of example battery 2 was not inferior to that of the comparative group battery.
Example 3
1. Pretreatment of positive plate grid
Taking 6-DZF-20 positive grid, 1 as positive electrode, 10 parallel-connected positive electrodes, placing in sulfuric acid tank containing sulfuric acid solution with density of 1.10g/mL, charging with 2.7A current for 2hr, and passing through each parallel-connected positive grid with current density of 0.25A/m 2 And velvet lead is generated on the surfaces of the parallel positive grids. After the energization, the positive grid as the negative electrode is placed in water for storage.
2. Preparation of inner lead plaster
According to the total mass of the inner lead plaster, 81.77 percent of lead powder, 0.08 percent of polyester staple fiber and 0.16 percent of antimony trioxide are dry-mixed and stirred for 5 minutes, mixed with 8.18 percent of water at room temperature for 10 minutes, added with sulfuric acid which accounts for 9.81 percent of the mass ratio of the lead powder and has the density of 1.4g/mL, stirred and reacted for 15 minutes, and the reaction temperature is controlled to be not higher than 55 ℃, so that the inner lead plaster with the apparent specific gravity of 4.50g/mL is obtained.
3. Preparation of middle lead plaster
According to the total mass of the middle-layer lead plaster, 85.98% of lead powder, 0.09% of polyester staple fiber and 0.17% of stannous sulfate are dry-mixed and stirred for 5 minutes, 8.60% of water is added at room temperature for wet mixing for 10 minutes, 5.16% of sulfuric acid with the density of 1.4g/mL is added for stirring and reacting for 15 minutes, the reaction temperature is controlled to be not higher than 65 ℃, and the middle-layer lead plaster with the apparent specific gravity of 4.5g/mL is obtained.
4. Preparation of outer lead plaster
According to the total mass of the outer layer lead plaster, 87.19% of lead powder, 0.09% of polyester staple fiber, 0.17% of colloidal graphite, 0.17% of red lead and 0.17% of 4BS seed crystal are dry-mixed and stirred for 5 minutes, then 8.72% of hot water with the temperature of 90 ℃ is added under the condition of heat preservation for wet mixing for 10 minutes, finally sulfuric acid with the density of 1.4g/mL accounting for 3.49% of the mass ratio of the lead powder is added for stirring and reacting for 20 minutes, the reaction temperature is controlled to be not lower than 85 ℃, and the outer layer lead plaster with the apparent specific gravity of 4.50g/mL is obtained.
5. Positive plate and battery fabrication
Taking out the 6-DZF-20 positive grid stored in water after pretreatment, coating inner lead plaster firstly, then coating middle lead plaster and outer lead plaster on one surface of the positive grid in sequence, turning the pole piece to the other surface, and coating the middle lead plaster and the outer lead plaster in sequence. Wherein, the coating quality of inlayer lead plaster is 66.0g, and the total quality of coating of middle level lead plaster (including the total quality of two sides coating, the same below) is 165g, and the total quality of coating of outer lead plaster is 99g, and inlayer lead plaster amount, middle level lead plaster amount and outer lead plaster amount account for respectively anodal lead plaster total mass to account for the ratio respectively: 20%, 50% and 30%. After coating, the raw positive plate is manufactured through surface acid spraying, surface drying, curing, drying and slitting. The green positive plate was taken for continuous drop test strength (results are shown in table 6). The positive plate, the negative plate and the separator are assembled into a semi-finished battery, and the semi-finished battery is formed into an experimental battery 3 through the procedures of formation and the like.
The porosity and composition of 3 pastels (results are shown in table 5), the 2HR capacity of the cell, the composition of the plate after discharge and the 100% DoD cycle life of the cell (results are shown in table 6).
Comparative example 9
1. Positive plate and battery fabrication
The inner lead plaster in example 3 was coated on the pretreated 6-DZF-20 positive grid in an amount of 330 g. After coating, the raw positive plate is manufactured through surface acid spraying, surface drying, curing, drying and slitting. The green positive plates were taken and tested for drop strength (results are shown in table 6). The positive plate, the negative plate and the separator are assembled into a semi-finished battery, and the comparative battery 9 is manufactured through the procedures of formation and the like.
The cell had a 2HR capacity, plate composition after discharge and 100% DoD cycle life (results are shown in table 6).
Comparative example 10
1. Positive plate and battery fabrication
The middle lead plaster in the embodiment 3 is coated on the pretreated 6-DZF-20 positive grid, and the coating amount is 330 g. After coating, the raw positive plate is manufactured through surface acid spraying, surface drying, curing, drying and slitting. The green positive plate was taken and tested for drop strength (results are shown in table 6). The positive plate, the negative plate and the separator are assembled into a semi-finished battery, and the comparative battery 10 is manufactured through the processes of formation and the like.
The 2HR capacity, plate composition after discharge and 100% DoD cycle life of the cell (results are shown in table 6).
Comparative example 11
1. Positive plate and battery fabrication
The outer lead plaster in example 3 was coated on the pretreated 6-DZF-20 positive grid in an amount of 330 g. After the coating is finished, the raw positive plate is manufactured through surface acid spraying, surface drying, curing, drying and slitting. The green positive plate was taken and tested for drop strength (results are shown in table 6). And assembling the positive plate, the negative plate and the partition plate into a semi-finished battery, and forming the semi-finished battery into a comparative battery 11.
The 2HR capacity, plate composition after discharge and 100% DoD cycle life of the cell (results are shown in table 6).
Comparative example 12
1. Positive plate and battery fabrication
According to the scheme disclosed by patent document CN109273716A, the middle-layer lead plaster in the embodiment 3 is coated on the pretreated 6-DZF-20 positive grid, the coating amount is 220g, then the outer-layer lead plaster in the embodiment 3 is respectively coated on two sides of the middle-layer lead plaster, the coating amount of each side is 55g, and the mass ratio of the middle-layer lead plaster amount to the total amount of the outer-layer lead plaster coated twice is 2: 1. After the coating is finished, the raw positive plate is manufactured through surface acid spraying, surface drying, curing, drying and slitting. The green positive plates were taken and tested for drop strength (results are shown in table 6). And assembling the positive plate, the negative plate and the partition plate into a semi-finished battery, and forming the semi-finished battery into a comparative battery 12.
The 2HR capacity, plate composition after discharge and 100% DoD cycle life of the cell (results are shown in table 6).
Table 5 lead paste porosity and composition test results in example 3
TABLE 6 Pole plate and Battery test data
From table 5, it can be seen that the porosity of the inner lead paste is the highest, the porosity of the middle lead paste is the second highest, the porosity of the outer lead paste is the lowest, and the contact areas of the outer electrode plate and the inner electrode plate reacting with sulfuric acid increase sequentially.
As can be seen from table 6, the positive plate fabricated in example 3 lost the least amount of active material in the plate drop test, and the strength was much stronger than that of the comparative positive plate, indicating that the binding force between the pre-treated grid and the active material of the positive plate was stronger; the 2HR capacity and the positive plate active material utilization rate of the battery 3 in the example are respectively 6.8%, 13.8%, 18.0% and 16.7% higher than those of comparative examples 9 to 12, and the positive plate active material utilization rate and the active material conversion rate are greatly improved; the battery life of example battery 3 was 81.6%, 25.3%, 12.9%, and 19.8% higher than that of comparative examples 9 to 12, respectively, and the life of example battery 3 was superior to that of the comparative group battery.
Claims (8)
1. A positive plate of a lead storage battery comprises a positive plate grid and positive lead plaster coated on the positive plate grid, and is characterized in that the positive lead plaster comprises inner lead plaster coated on the positive plate grid, middle lead plaster coated on two sides of the inner lead plaster and outer lead plaster coated on the outer sides of the middle lead plaster on two sides,
(1) the inner lead plaster comprises the following components in percentage by mass: 22.7-28.6% of 1BS, 42.7-44.2% of 3BS, 2.8-4.0% of alpha-PbO, 14.1-22.0% of beta-PbO and 8.6-9.2% of Pb;
(2) the middle lead plaster comprises the following components in percentage by mass: 57.3-67.2% of 3BS, 22.7-30.2% of alpha-PbO, 1.2-3.4% of beta-PbO and 8.2-9.1% of Pb;
(3) the outer lead plaster comprises the following components in percentage by mass: 3.2 to 9.3 percent of 3BS, 2.0 to 3.7 percent of alpha-PbO, 11.3 to 21.9 percent of beta-PbO, 56.2 to 73.7 percent of 4BS and 8.6 to 9.2 percent of Pb,
the porosity of the inner layer lead plaster is 45.2-48.3%, the porosity of the middle layer lead plaster is 40.6-43.2%, and the porosity of the outer layer lead plaster is 38.0-41.6%.
2. The positive plate for a lead-acid battery as claimed in claim 1, wherein the coating mass of the inner lead paste, the middle lead paste and the outer lead paste is 10 to 20%, 45 to 60% and 25 to 45% of the total mass of the positive lead paste.
3. The positive plate of lead-acid battery as claimed in claim 1, wherein the inner lead plaster comprises, in terms of total mass percent of the inner lead plaster, 79.81-83.13% of lead powder, 0.08% of polyester staple fiber, 0.17% of antimony trioxide or stannous sulfate, 7.97-8.31% of water and 8.31-11.97% of sulfuric acid with density of 1.4g/mL,
the preparation method of the inner lead plaster comprises the following steps:
lead powder, polyester staple fiber, antimony trioxide or stannous sulfate are dry-mixed and stirred for 5 minutes, water is added at room temperature for wet mixing for 10 minutes, sulfuric acid with the density of 1.4g/mL is added for stirring and reaction for 15 minutes, the reaction temperature is controlled to be not higher than 55 ℃, and inner-layer lead plaster with the apparent specific gravity of 4.5g/mL is obtained.
4. The positive plate of lead storage battery as claimed in claim 1, wherein the raw material of the middle lead plaster comprises 84.53-87.49% of lead powder, 0.09% of polyester staple fiber, 0.17% of antimony trioxide or stannous sulfate, 8.45-8.75% of water and 3.50-6.76% of sulfuric acid with a density of 1.4g/mL,
the preparation method of the middle-layer lead plaster comprises the following steps:
lead powder, polyester staple fiber, antimony trioxide or stannous sulfate are dry-mixed and stirred for 5 minutes, water is added at room temperature for wet mixing for 10 minutes, sulfuric acid with the density of 1.4g/mL is added for stirring and reaction for 15 minutes, the reaction temperature is controlled to be not higher than 65 ℃, and the middle-layer lead plaster with the apparent specific gravity of 4.5g/mL is obtained.
5. The positive plate of lead-acid battery as claimed in claim 1, wherein the raw material of the outer lead plaster comprises, in terms of the total mass percentage of the outer lead plaster, 85.69-88.73% of lead powder, 0.09% of polyester staple fiber, 0.17% of colloidal graphite, 0.17-0.18% of red lead, 0.17-0.18% of 4BS seed crystal, 8.57-8.87% of water and 1.78-5.14% of sulfuric acid with a density of 1.4g/mL,
the preparation method of the outer lead plaster comprises the following steps:
the lead powder, the polyester staple fibers, the colloidal graphite, the red lead and the 4BS seed crystal are mixed in a dry mode and stirred for 5 minutes, then hot water at 90 ℃ is added under the heat preservation condition to be mixed in a wet mode for 10 minutes, finally sulfuric acid with the density of 1.4g/mL is added to be stirred and reacted for 15-30 minutes, the reaction temperature is controlled to be not lower than 85 ℃, and the outer-layer lead plaster with the apparent specific gravity of 4.5g/mL is obtained.
6. The positive plate for a lead-acid battery as claimed in claim 1, wherein the positive plate grid is pretreated with a layer of de-oxidation.
7. The positive plate of lead-acid battery as claimed in claim 6, wherein the positive plate grid is placed in a sulfuric acid tank containing 1.05-1.15 g/mL sulfuric acid solution, and charged for 0.5-5 hours, and the current density passing through each positive plate grid in parallel is 0.1-0.5A/m 2 And velvet lead is generated on the surfaces of the parallel positive grids.
8. A lead-acid battery comprising the positive electrode plate for a lead-acid battery as defined in any one of claims 1 to 7.
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| JPH0793135B2 (en) * | 1988-05-30 | 1995-10-09 | 新神戸電機株式会社 | Lead acid battery and manufacturing method thereof |
| US5252105A (en) * | 1992-10-06 | 1993-10-12 | General Motors Corporation | Method of forming lead-acid battery electrode |
| CN103762359A (en) * | 2014-01-10 | 2014-04-30 | 超威电源有限公司 | Positive lead plaster for lead-acid storage battery |
| CN106252655B (en) * | 2016-08-30 | 2018-02-23 | 超威电源有限公司 | A kind of lead-acid accumulator anode diachylon prepared using α PbO |
| CN106711531A (en) * | 2016-12-21 | 2017-05-24 | 东南大学 | Method for preparing basic lead sulfates from PbO and producing lead-acid battery from basic lead sulfates |
| CN108550854B (en) * | 2018-05-11 | 2020-12-25 | 天能电池集团股份有限公司 | Positive lead plaster of lead storage battery and preparation method thereof |
| CN109273716B (en) * | 2018-08-16 | 2020-04-03 | 天能电池集团股份有限公司 | Long-life lead storage battery and preparation method thereof |
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