阅读说明：本技术 长寿命高比能量免维护起动铅酸蓄电池及其生产方法 (Maintenance-free starting lead-acid storage battery with long service life and high specific energy and production method thereof ) 是由 高国兴 史俊雷 余萍 庞雨雨 王倩 徐建刚 张祖波 于 2019-06-24 设计创作，主要内容包括：一种长寿命高比能量免维护起动铅酸蓄电池及其生产方法,其正极板、负极板中至少有一类极板的板栅上部、下部涂覆的铅膏不同,板栅下部的铅膏导电性或利用率优于板栅上部的铅膏的导电性或利用率。极板采用上部、下部不一样的配方、分别涂填,下部通过铅膏的含酸量不同,降低了铅膏视密度或者导电物质含量不同提高其利用率,有效改善了下部活性物质利用率低的问题,提高了电池的容量,同时下部内阻降低、利用率提高减缓了上部放电量比例高的问题,在同样放电量的情况下,极板上部放电量下降,放电倍率下降,故活性物质软化脱落会降低,延长了电池使用寿命。本发明制备的电池,在同样涂膏量的情况下,容量、低温放电性能、循环耐久性能得到了提升。(The lead-acid accumulator has at least one kind of positive plate and negative plate with different coated lead pastes, and the lead paste in the lower part of the plate grid has higher conductivity and utilization rate than that in the upper part of the plate grid. The polar plate adopts different formulas of the upper part and the lower part to be respectively coated and filled, the acid content of the lead plaster is different at the lower part, the apparent density of the lead plaster is reduced or the content of conductive substances is different, the utilization rate of the lead plaster is improved, the problem of low utilization rate of active substances at the lower part is effectively solved, the capacity of the battery is improved, meanwhile, the problem of high proportion of upper discharge capacity is solved by reducing the internal resistance at the lower part and improving the utilization rate, under the condition of the same discharge capacity, the upper discharge capacity of the polar plate is reduced, the discharge multiplying power is reduced, so that the softening and falling of the active substances are reduced. The battery prepared by the invention has improved capacity, low-temperature discharge performance and cycle durability under the condition of the same paste amount.)

1. The utility model provides a long-life high specific energy non-maintaining starts lead acid battery, includes polar plate, barrier film, electrolyte and battery case, and the polar plate includes grid and grid surface coating's lead plaster, its characterized in that: the polar plates are divided into two types of polar plates, namely a positive plate and a negative plate, the upper part and the lower part of a grid of at least one type of polar plates in the positive plate and the negative plate are coated with different lead pastes, and the conductivity or the utilization rate of the lead paste at the lower part of the grid is superior to that of the lead paste at the upper part of the grid.

2. The utility model provides a long-life high specific energy non-maintaining start lead acid battery which characterized in that: the lead pastes coated on the upper part and the lower part of the grid of at least one type of the positive plate and the negative plate have different acid contents and/or different apparent densities or different conductive substance contents.

3. The long life high specific energy maintenance-free lead acid battery of claim 2, wherein: the positive plate comprises a grid and positive lead plaster coated on the surface of the grid, the positive lead plaster is a first positive lead plaster and a second positive lead plaster, the first positive lead plaster is coated on the surface of the upper part of the grid, and the second positive lead plaster is coated on the surface of the lower part of the grid; the components by mass percentage are as follows:

the first positive electrode lead paste comprises the following components: 0.05-0.12% of short fibers, 2-15% of red lead, 0.4-1.5% of 4BS seeds, 8-14% of pure water and 1.38g/cm³6-12% of sulfuric acid solution and the balance of lead powder;

the second positive electrode lead paste comprises the following components: 0.05-0.12% of short fibers, 2-15% of red lead, 0.4-1.5% of 4BS seeds, 8-14% of pure water and 1.38g/cm³10-15% of sulfuric acid solution and the balance of lead powder;

the upper portion proportion of a grid of the positive plate is 40% -70%, and the lower portion proportion of the grid is 30% -60%.

4. The long life high specific energy maintenance-free lead acid battery of claim 2, wherein:the first positive electrode lead paste comprises the following components: 0.07-0.09% of short fiber, 7-10% of red lead, 0.8-1.2% of 4BS seed, 9-11% of pure water and 1.38g/cm³8-10% of sulfuric acid solution and the balance of lead powder;

the second positive electrode lead paste comprises the following components: 0.07-0.09% of short fiber, 7-10% of red lead, 0.8-1.2% of 4BS seed, 0.05-0.5% of conductive carbon black, 9-11% of pure water and 1.38g/cm³8-10% of sulfuric acid solution and the balance of lead powder.

5. The long life high specific energy maintenance-free lead acid battery of claim 1, wherein: the negative plate comprises a grid and negative lead plaster coated on the surface of the grid, the negative lead plaster is a first negative lead plaster and a second negative lead plaster, the first negative lead plaster is coated on the surface of the upper part of the grid, and the second negative lead plaster is coated on the surface of the lower part of the grid; the components by mass percentage are as follows:

the first negative lead paste comprises the following components: 0.2-0.4% of carbon black, 0.05-0.1% of short fibers, 0.1-0.3% of lignin, 0.5-1.0% of barium sulfate, 8-12% of pure water and 1.38g/cm³7-12% of sulfuric acid solution and the balance of lead powder;

the second negative lead plaster comprises the following components: 0.2-0.4% of carbon black, 0.06-0.12% of short fibers, 0.1-0.3% of lignin, 0.5-1.0% of barium sulfate, 9-14% of pure water and 1.38g/cm³8-14% of sulfuric acid solution and the balance of lead powder;

the upper portion proportion of a grid of the negative plate is 40% -70%, and the lower portion proportion of the grid is 30% -60%.

6. The long life high specific energy maintenance-free lead acid battery of claim 5, wherein: the first negative lead paste comprises the following components: 0.2-0.3% of carbon black, 0.06-0.08% of short fiber, 0.2-0.3% of lignin, 0.6-0.8% of barium sulfate, 8-10% of pure water and 1.38g/cm³8-10% of sulfuric acid solution and the balance of lead powder;

the second negative lead plaster comprises the following components: 0.2-0.3% of carbon black, 0.1-0.2% of conductive carbon fiber, 0.06-0.08% of short fiber, 0.2-0.3% of lignin, 0.6-0.8% of barium sulfate, 8-10% of pure water and 1.38g/cm³8-10% of sulfuric acid solution and the balance of lead powder.

7. A method of producing a long life high specific energy maintenance-free lead acid battery as claimed in any one of claims 1 to 6, characterized by comprising the steps of:

1) preparing a positive plate;

2) preparing a negative plate;

3) a clapboard:

the partition board is a low-resistance PE partition board;

4) assembling the battery:

stacking the positive plate, the negative plate and the partition plate into a plate group by an encapsulation machine, then carrying out cast welding on the plate group, putting the plate group into a battery jar after the cast welding, and assembling into a qualified semi-finished battery through butt welding, heat sealing, air tightness detection and the like;

5) formation of a battery:

the qualified semi-finished battery is assembled by adding acid for one time, wherein the acid is analytically pure sulfuric acid with the density of 1.1-1.3 g/ml, the battery is formed by electrifying within half an hour after the acid is added, and acid liquor is poured out after the formation is finished;

6) and (3) secondary acid addition:

adding acid for the second time of the battery with the acid liquid poured off, wherein the acid liquid is 1.27-1.35 g/cm³Analyzing pure sulfuric acid, and adding a metal sulfate additive with the mass fraction of 0.3% -2%.

8. The method of claim 7, wherein the step 1) of preparing the positive plate comprises preparing a first positive paste and preparing a second positive paste:

1) the preparation method of the first positive electrode lead paste comprises the following steps:

mechanically premixing red lead and 4BS seeds for 2-5 min, and uniformly mixing;

putting the auxiliary materials mixed in the step (1) and short fibers into lead powder, and carrying out dry stirring for 5-10 min;

adding pure water, and wet-stirring for 5-10 min;

slowly adding a sulfuric acid solution into the mixture obtained in the step (3), controlling the acid adding time to be 10-20 min, controlling the temperature not to exceed 65 ℃ in the process, and stirring for 10-20 min after the acid adding is finished;

mixing the pastes for later use;

2) the preparation method of the second anode lead paste comprises the following steps:

(1) mechanically premixing red lead and 4BS seeds for 2-5 min, and uniformly mixing;

(2) putting the auxiliary materials mixed in the step (1) and short fibers into lead powder, and carrying out dry stirring for 5-10 min;

(3) adding pure water, and wet-stirring for 5-10 min;

(4) slowly adding the sulfuric acid solution into the mixture obtained in the step (3), controlling the acid adding time to be 10-20 min, controlling the temperature not to exceed 65 ℃ in the process, stirring for 10-20 min after the acid adding is finished,

(5) mixing the pastes for later use;

3) coating and filling a positive plate:

and dividing the prepared grid into an upper part and a lower part, coating and filling the upper part of the grid with a first positive lead plaster and coating and filling the lower part of the grid with a second positive lead plaster, and curing and drying after coating and filling to obtain the positive plate.

9. The method for producing a long-life high-specific energy maintenance-free starting lead-acid storage battery according to claim 7, wherein the step 2) of preparing the negative plate comprises the steps of preparing a first negative electrode lead paste and preparing a second negative electrode lead paste:

1) the preparation method of the first negative electrode lead paste comprises the following steps:

(1) mechanically premixing carbon black, lignin and barium sulfate for 5-10 min, and uniformly mixing;

(2) adding the auxiliary materials mixed in the step (1) and short fibers into lead powder, and carrying out dry stirring for 3-10 min;

(3) adding pure water into the mixture obtained in the step (2), and carrying out wet stirring for 5-10 min;

(4) slowly adding a sulfuric acid solution into the mixture obtained in the step (3), controlling the acid adding time to be 10-20 min, controlling the temperature not to exceed 65 ℃ in the process, and stirring for 10-20 min after the acid adding is finished;

(5) mixing the pastes for later use;

2) the preparation of the second negative electrode lead paste comprises the following steps:

(1) mechanically premixing carbon black, lignin and barium sulfate for 5-10 min, and uniformly mixing;

(2) adding the auxiliary materials mixed in the step (1) and short fibers into lead powder, and carrying out dry stirring for 3-10 min;

(3) adding pure water into the mixture obtained in the step (2), and carrying out wet stirring for 5-10 min;

(4) slowly adding a sulfuric acid solution into the mixture obtained in the step (3), controlling the acid adding time to be 10-20 min, controlling the temperature not to exceed 65 ℃ in the process, and stirring for 10-20 min after the acid adding is finished;

(5) mixing the pastes for later use;

3) coating and filling a negative plate:

and dividing the prepared grid into an upper part and a lower part, coating and filling the upper part of the grid with first negative lead plaster, coating and filling the lower part of the grid with second negative lead plaster, and curing and drying after coating to obtain the negative plate.

10. The method for producing a long life high specific energy maintenance-free lead acid battery as claimed in claim 7, wherein in the step 6) of secondary acid addition, the metal sulfate additive is two or more of sodium sulfate, zinc sulfate and magnesium sulfate.

Technical Field

The invention belongs to the field of storage batteries, and particularly relates to a maintenance-free starting lead-acid storage battery with long service life and high specific energy.

Background

The lead-acid storage battery mainly comprises a positive plate, a negative plate, a partition plate, a busbar, electrolyte, a tank cover and the like. The polar plate is the core component of the lead-acid storage battery, the performance of the polar plate directly affects the performance and the service life of the battery, and the polar plate is usually composed of a grid and lead paste. The lead plaster mainly plays a role in providing energy storage and output in the charging and discharging process, is the most important active substance to directly participate in the reaction, and is a key factor influencing the performance of the storage battery. Lead plaster generally consists of lead powder, sulfuric acid, pure water, additives (such as short fibers and lignin) and the like, and an active substance carrier with a certain porosity and excellent charge and discharge performance is formed through a proper paste mixing process, coating, filling, curing and drying.

In the use process of the lead-acid storage battery, the defects of low utilization rate, insufficient charging, sulfation, battery performance reduction, short service life of the lead-acid storage battery and the like generally exist. In order to solve the above technical problems, the current solutions of manufacturing enterprises generally achieve the increase of the service life by increasing the amount of lead paste and reducing the utilization rate of active substances, and the prior art solutions have the following disadvantages: 1. the weight and the lead consumption of the battery are improved by increasing the lead paste amount, the capacity is increased, but the cost is also increased; 2. the active utilization is reduced by formulation adjustments, but the capacity is reduced and the amount of paste is increased if the rated capacity is not met.

Disclosure of Invention

The invention solves the problem of providing a maintenance-free starting lead-acid storage battery with low cost, high utilization rate of active substances, long service life and high specific energy.

The invention also aims to provide a production method of the maintenance-free starting lead-acid storage battery with long service life and high specific energy.

The technical idea of the invention is that the current is transmitted according to the path of the minimum ohm internal resistance preferentially when discharging because of the ohm internal resistance in the charging and discharging process of the battery, and the upper part of the polar plate reacts preferentially to bear most of the discharging electricity quantity, especially in the shallow discharging circulation because the upper part of the battery is provided with the bus bar for collecting the current. Similarly, the lower part of the polar plate is difficult to charge than the upper part during charging. This leads to a problem that the utilization rate of the upper active material is high and the utilization rate of the lower active material is low during use. In the process of charging and discharging, the positive lead plaster is mutually converted between lead sulfate and lead, the negative lead plaster is mutually converted between lead dioxide and lead sulfate, and the lead plaster continuously shrinks and expands due to different molar volumes.

Due to the high utilization rate of the active substance on the upper part, the active substance on the upper part is easy to soften and fall off, the service life of the battery is shortened, and the terminal customer is not satisfied. In the use process, due to the ohmic internal resistance, the utilization rate of the lower part of the polar plate is obviously lower than that of the upper part of the polar plate during discharging, and the lower part of the polar plate is later than that of the upper part of the polar plate during charging, so that the lower polar plate is more prone to low utilization rate and insufficient charging to generate a sulfation phenomenon, and the performance of the battery is reduced.

The lead plaster formula coated on the grid of at least one kind of polar plate in the positive plate and the negative plate is different, so that the conductivity of the lead plaster at the lower part of the grid is better than that at the upper part of the grid, the utilization rate of active substances at the upper part and the lower part of the grid is close, the service life of the storage battery is prolonged, and the storage battery has the advantages of long service life and high specific energy.

The technical scheme includes that the battery comprises a polar plate, a separation film, electrolyte and a battery shell, wherein the polar plate comprises a grid and lead plaster coated on the surface of the grid, the polar plate is divided into a positive plate and a negative plate, the lead plaster coated on the upper part and the lower part of the grid of at least one type of the positive plate and the negative plate is different, and the conductivity or the utilization rate of the lead plaster on the lower part of the grid is superior to that of the lead plaster on the upper part of the grid.

The lead pastes coated on the upper part and the lower part of the grid of at least one type of the positive plate and the negative plate have different acid contents and/or different apparent densities or different conductive substance contents.

The positive plate comprises a grid and positive lead plaster coated on the surface of the grid, wherein the positive lead plaster is a first positive lead plaster and a second positive lead plaster; the components by mass percentage are as follows:

the first positive electrode lead paste comprises the following components: 0.05-0.12% of short fibers, 2-15% of red lead, 0.4-1.5% of 4BS seeds, 8-14% of pure water and 1.38g/cm³6-12% of sulfuric acid solution and the balance of lead powder; after the paste mixing is finished, the apparent density is 4.0-4.7 g/ml;

the second positive electrode lead paste comprises the following components: 0.05-0.12% of short fibers, 2-15% of red lead, 0.4-1.5% of 4BS seeds, 8-14% of pure water and 1.38g/cm³10-15% of sulfuric acid solution and the balance of lead powder; after the paste mixing is finished, the apparent density is 3.8-4.4 g/ml;

the proportion of the upper part of a grid of the positive plate is 40-70%, and the proportion of the lower part of the grid is 30-60%.

Alternatively, the first positive electrode lead paste of the present invention may also have a composition of: 0.07-0.09% of short fiber, 7-10% of red lead, 0.8-1.2% of 4BS seed, 9-11% of pure water and 1.38g/cm³8-10% of sulfuric acid solution and the balance of lead powder;

the second positive electrode lead paste can also consist of: 0.07-0.09% of short fiber, 7-10% of red lead, 0.8-1.2% of 4BS seed, 0.05-0.5% of conductive carbon black, 9-11% of pure water and 1.38g/cm³8-10% of sulfuric acid solution and the balance of lead powder.

The negative plate comprises a grid and negative lead plaster coated on the surface of the grid, wherein the negative lead plaster is a first negative lead plaster and a second negative lead plaster; the components by mass percentage are as follows:

the first negative lead paste comprises the following components: 0.2-0.4% of carbon black, 0.05-0.1% of short fibers, 0.1-0.3% of lignin, 0.5-1.0% of barium sulfate, 8-12% of pure water and 1.38g/cm³7-12% of sulfuric acid solution and the balance of lead powder; after the paste mixing, the apparent density is 4.0-4.5 g/ml;

the second negative lead plaster comprises the following components: 0.2-0.4% of carbon black, 0.06-0.12% of short fibers, 0.1-0.3% of lignin, 0.5-1.0% of barium sulfate, 9-14% of pure water and 1.38g/cm³8-14% of sulfuric acid solution and the balance of lead powder; after the paste mixing is finished, the apparent density is 3.8-4.4 g/ml;

the proportion of the upper part of a grid of the negative plate is 40-70%, and the proportion of the lower part of the grid is 30-60%.

Or, the first negative electrode lead paste of the invention may also comprise: 0.2-0.3% of carbon black, 0.06-0.08% of short fiber, 0.2-0.3% of lignin, 0.6-0.8% of barium sulfate, 8-10% of pure water and 1.38g/cm³8-10% of sulfuric acid solution and the balance of lead powder;

the second negative electrode lead paste can also consist of: 0.2-0.3% of carbon black, 0.1-0.2% of conductive carbon fiber, 0.06-0.08% of short fiber, 0.2-0.3% of lignin, 0.6-0.8% of barium sulfate, 8-10% of pure water and 1.38g/cm³8-10% of sulfuric acid solution and the balance of lead powder.

The invention relates to a production method of a maintenance-free starting lead-acid storage battery with long service life and high specific energy, which comprises the following working procedures:

1) preparing a positive plate;

2) preparing a negative plate;

3) a clapboard:

the partition board is a low-resistance PE partition board;

4) assembling the battery:

stacking the positive plate, the negative plate and the partition plate into a plate group by an encapsulation machine, then carrying out cast welding on the plate group, putting the plate group into a battery jar after the cast welding, and assembling into a qualified semi-finished battery through butt welding, heat sealing, air tightness detection and the like;

5) formation of a battery:

the qualified semi-finished battery is assembled by adding acid for one time, wherein the acid is analytically pure sulfuric acid with the density of 1.1-1.3 g/ml, the battery is formed by electrifying within half an hour after the acid is added, and acid liquor is poured out after the formation is finished;

6) and (3) secondary acid addition:

adding acid for the second time of the battery with the acid liquid poured off, wherein the acid liquid is 1.27-1.35 g/cm³Analytically pure sulfuric acid, and metal sulfate with the mass fraction of 0.3% -2% is addedAnd (3) preparing.

In the step 6) of the production method of the invention, in the secondary acid adding, the metal sulfate additive is two or more of sodium sulfate, zinc sulfate and magnesium sulfate.

The production method comprises the following steps of 1), preparing the positive plate, namely preparing the first positive lead paste and preparing the second positive lead paste:

1) the preparation method of the first positive electrode lead paste comprises the following steps:

(1) mechanically premixing red lead and 4BS seeds for 2-5 min, and uniformly mixing;

(2) putting the auxiliary materials mixed in the step (1) and short fibers into lead powder, and carrying out dry stirring for 5-10 min;

(3) adding pure water, and wet-stirring for 5-10 min;

(4) slowly adding a sulfuric acid solution into the mixture obtained in the step (3), controlling the acid adding time to be 10-20 min, controlling the temperature not to exceed 65 ℃ in the process, and stirring for 10-20 min after the acid adding is finished;

(5) mixing the pastes for later use;

2) the preparation method of the second anode lead paste comprises the following steps:

(1) mechanically premixing red lead and 4BS seeds for 2-5 min, and uniformly mixing;

(2) putting the auxiliary materials mixed in the step (1) and short fibers into lead powder, and carrying out dry stirring for 5-10 min;

(3) adding pure water, and wet-stirring for 5-10 min;

(4) slowly adding the sulfuric acid solution into the mixture obtained in the step (3), controlling the acid adding time to be 10-20 min, controlling the temperature not to exceed 65 ℃ in the process, stirring for 10-20 min after the acid adding is finished,

(5) mixing the pastes for later use;

3) coating and filling a positive plate:

and dividing the prepared grid into an upper part and a lower part, coating and filling the upper part of the grid with a first positive lead plaster and coating and filling the lower part of the grid with a second positive lead plaster, and curing and drying after coating and filling to obtain the positive plate.

The step 2) of the production method comprises the following steps:

1) the preparation method of the first negative electrode lead paste comprises the following steps:

(1) mechanically premixing carbon black, lignin and barium sulfate for 5-10 min, and uniformly mixing;

(2) adding the auxiliary materials mixed in the step (1) and short fibers into lead powder, and carrying out dry stirring for 3-10 min;

(3) adding pure water into the mixture obtained in the step (2), and carrying out wet stirring for 5-10 min;

(4) slowly adding a sulfuric acid solution into the mixture obtained in the step (3), controlling the acid adding time to be 10-20 min, controlling the temperature not to exceed 65 ℃ in the process, and stirring for 10-20 min after the acid adding is finished;

(5) after the paste mixing is finished;

2) the preparation of the second negative electrode lead paste comprises the following steps:

(1) mechanically premixing carbon black, lignin and barium sulfate for 5-10 min, and uniformly mixing;

(2) adding the auxiliary materials mixed in the step (1) and short fibers into lead powder, and carrying out dry stirring for 3-10 min;

(3) adding pure water into the mixture obtained in the step (2), and carrying out wet stirring for 5-10 min;

(4) slowly adding a sulfuric acid solution into the mixture obtained in the step (3), controlling the acid adding time to be 10-20 min, controlling the temperature not to exceed 65 ℃ in the process, and stirring for 10-20 min after the acid adding is finished;

(5) after the paste mixing is finished;

3) coating and filling a negative plate:

and dividing the prepared grid into an upper part and a lower part, coating and filling the upper part of the grid with first negative lead plaster, coating and filling the lower part of the grid with second negative lead plaster, and curing and drying after coating to obtain the negative plate.

Compared with the prior art, the maintenance-free lead-acid storage battery provided by the invention has the following advantages:

1. the polar plate adopts a formula with different upper parts and lower parts, the polar plate adopts the upper part and the lower part to be coated and filled respectively, and the lower part has different acid contents through lead plaster, thereby reducing the apparent density of the lead plaster or improving the utilization rate of the lead plaster due to different contents of conductive substances. For example, the lower part adopts the lead paste with low apparent density, the porosity is increased, and the sulfuric acid is more favorably immersed and diffused, so the ohmic internal resistance is reduced, the problem of low utilization rate of active substances at the lower part is effectively solved, and the capacity of the battery is improved. Meanwhile, the lower internal resistance is reduced, the utilization rate is improved, the problem of high proportion of upper discharge capacity is solved, the upper discharge capacity of the polar plate is reduced under the condition of the same discharge capacity, the discharge rate is reduced, the softening and falling of active substances are reduced, and the service life of the battery is prolonged.

2. The battery performance data is that under the condition of the same paste coating amount, the 20h capacity (GB/T5008-.

Detailed Description