Long life valve regulated explosion proof power type lead acid battery and method of manufacturing the same

Abstract

The application belongs to the technical field of lead-acid storage batteries, and particularly relates to a long-life valve-regulated explosion-proof power type lead-acid storage battery and a manufacturing method thereof. The long-life valve-regulated explosion-proof power type lead-acid storage battery provided by the application is characterized in that the positive grid of the battery is cast by using a nine-element alloy of lead, antimony, arsenic, tin, selenium, copper, lanthanum, aluminum and silicon; the positive grid structure is designed in a plate type, the thickness of the upper half is greater than that of the lower half, the vertical ribs and the horizontal ribs of the positive grid are in an elliptical or semi-elliptical shape, and a frame is arranged on the outer side; the separator is in an S-shaped structure, the edges of the grid are alternately opened on both sides, the bottom is fully opened, the upper part of the grid is semi-opened, and the S-shaped structure covers the positive plate and the negative plate. The application provides the valve-regulated explosion-proof power type lead-acid storage battery with long life, high corrosion resistance, lead-antimony short-circuit prevention and controllable cost, and further provides a manufacturing method thereof.

Description

Technical Field

[0001] This invention belongs to the field of lead-acid battery technology, specifically relating to a long-life valve-regulated explosion-proof power lead-acid battery and its manufacturing method. Background Technology

[0002] Valve-regulated explosion-proof lead-acid batteries are widely used in electric vehicles and energy storage due to their mature manufacturing process, excellent low-temperature performance, high safety, and maintenance-free operation. However, their cycle durability is typically only 300 to 600 cycles, which is 40% to 70% lower than that of tubular lead-acid batteries, indicating significant room for improvement. This shortcoming mainly stems from two failure modes: during long-term charge-discharge cycles, the positive electrode grid (especially in the upper and middle regions with higher current density) will corrode and fracture, leading to degradation of the conductive network and capacity decay; simultaneously, lead dendrites generated at the negative electrode may deposit at the positive electrode lugs, causing micro-short circuits and accelerating battery failure. These two problems severely limit the battery's lifespan in deep-cycle applications.

[0003] To improve cycle life, existing technologies have been improved from multiple angles, but all have limitations. Regarding positive electrode grid materials, corrosion resistance is mainly improved through alloying, such as using cadmium-free lead-antimony-arsenic-tin-copper-selenium multi-element alloys, or adding rare earth elements (such as lanthanum) to refine grains and enhance corrosion resistance. However, these material improvements mostly focus on enhancing the intrinsic properties of the alloy, and are insufficient in providing targeted protection against localized corrosion caused by uneven current distribution during cycling, especially corrosion in the high-stress areas of the upper and middle sections.

[0004] Regarding the design of the grid and electrode structure, CN117525441A discloses a grid structure for lead-acid batteries. This structure enhances overall mechanical rigidity by incorporating reinforcing ribs and integrated reinforcing strips within the grid, reducing deformation and active material shedding. However, it primarily addresses mechanical support and deformation resistance, offering limited relief for the electrochemical corrosion process. Corrosion of the tetrahedral lead ribs initiates preferentially from the edges, exhibiting localized acceleration, with the failure mode being "point-to-surface" corrosion fracture. CN111081985A discloses a zoned paste coating technology, applying lead pastes of different formulations to the upper and lower parts of the positive electrode grid to improve reaction uniformity under high current operation and alleviate active material softening. These structural optimizations are effective in inhibiting material shedding, but they fail to fundamentally delay the electrochemical corrosion process of the grid body.

[0005] In terms of manufacturing processes, research focuses on precise temperature control and stirring during alloy melting, as well as parameter optimization in the paste mixing process, aiming to improve battery consistency and production efficiency. These process improvements are supplementary measures, and their lifespan extension effect is limited by the battery's fundamental design and material system.

[0006] Therefore, existing improvement solutions mostly adopt a "single-point breakthrough" approach, focusing on materials, structure, or process optimization, lacking a systematic approach. Battery cycle life is a complex issue determined by multiple failure mechanisms, including grid corrosion, active material shedding, and lead dendrite short circuits. Improvements in a single dimension cannot comprehensively address all problems, particularly failing to simultaneously achieve effective suppression of corrosion in critical grid areas, overall optimization of the active material structure, and root-cause prevention of dendrite growth. Summary of the Invention

[0007] The technical problem to be solved by the present invention is to overcome the above-mentioned defects of the prior art and provide a valve-regulated explosion-proof power lead-acid battery with long life, high corrosion resistance, prevention of lead wool short circuit and controllable cost. The present invention also provides a method for manufacturing it.

[0008] The long-life valve-regulated explosion-proof power lead-acid battery of the present invention has a positive grid made of a nine-element alloy of lead, antimony, arsenic, tin, selenium, copper, lanthanum, aluminum and silicon. The positive grid structure adopts a plate design, with the upper half being thicker than the lower half. The vertical and horizontal ribs of the positive grid are elliptical or semi-elliptical, and a frame is provided on the outside. The separator has an S-shaped structure, which covers the positive and negative plates.

[0009] The upper half of the positive plate grid has a thickness of 3~10mm, and the lower half has a thickness of 2~7mm.

[0010] The nine-element alloy of the positive grid has the following content by mass percentage: antimony 0.5~1.0, arsenic 0.05~0.20, tin 0.05~0.20, selenium 0.02~0.04, copper 0.03~0.04, lanthanum 0.01~0.02, aluminum 0.01~0.03, silicon 0.01~0.03, with lead as the balance.

[0011] The vertical ribs of the positive plate grid structure have elliptical cylinders with a minor axis of 3~10mm and a major axis of 4.5~15mm, and the horizontal ribs have elliptical cylinders with a minor axis of 1.5~5mm and a major axis of 3~10mm, forming a grid structure with an outer frame of 3~10mm thickness.

[0012] The separator has an S-shaped structure and is made of AGM. The plates of the grid have alternating openings on both sides of the edge, a full opening at the bottom, and a semi-open opening at the top. The S-shaped structure covers the positive plate, the negative plate, and the plate lugs.

[0013] The thickness of the S-type AGM partition is 0.8~4.0mm, the porosity of the partition is 65%~95%, and the average pore size is ≤22μm.

[0014] The top of the positive plate grid is provided with a plate lug, and the plate lug and the positive plate grid are integrally cast structures.

[0015] The battery is equipped with an explosion-proof battery compartment, the battery compartment and the battery cover are sealed by heat fusion, a sealing ring is press-fitted at the terminal position, and an exhaust valve is provided at the top.

[0016] The manufacturing method of the long-life valve-regulated explosion-proof power lead-acid battery includes the following steps:

[0017] (1) Preparation of positive grid: The positive grid is manufactured by gravity casting and is made of nine-element alloy;

[0018] (2) Preparation of positive electrode plate: The positive electrode lead paste is applied to the positive plate grid by paste application, and then cured and dried to obtain the positive electrode plate;

[0019] (3) Preparation of negative electrode plate: The negative electrode lead paste is applied to the negative plate grid by paste application, and then cured and dried to obtain the negative electrode plate;

[0020] (4) Preparation of positive and negative electrode groups: The positive and negative electrode groups are combined according to the rule of alternating positive and negative electrode plates. Then, lead-antimony alloy is used to complete the electrode group welding and electrode column casting by casting and welding technology. The separator first covers the negative electrode group and then covers the positive electrode group.

[0021] (5) Preparation of power type lead-acid battery: The positive electrode group and the negative electrode group are formed, and then placed into the explosion-proof battery case. The explosion-proof battery case and cover are heat-sealed, the terminal sealing ring is pressed in, and the exhaust valve is closed to obtain the power type lead-acid battery.

[0022] The specific process parameters for gravity casting in step (1) are: mold temperature 100~180℃, alloy melting temperature 430~560℃, casting speed 3~6 pieces / min, and water cooling for 5s.

[0023] Step (2) involves manufacturing a positive electrode lead paste using lead powder, red lead powder, sulfuric acid, water, and polypropylene fiber, with an apparent density of 4.2~4.6 g / cm³. 3 .

[0024] In step (2), the positive electrode lead paste is applied to the positive grid, with the upper half coated with a thickness of 4.5~6mm and the lower half coated with a thickness of 2.5~4mm.

[0025] The curing temperature of step (2) is 35℃, relative humidity is 90%, and the time is 48h. The drying temperature is 70℃, relative humidity is ≤10%, and the time is 48h.

[0026] Step (3) involves manufacturing a negative electrode lead paste using lead powder, sulfuric acid, water, polypropylene fiber, sodium lignosulfonate, carbon black, and barium sulfate, with an apparent density of 4.2~4.6 g / cm³. 3 .

[0027] The curing temperature of step (3) is 35℃, relative humidity is 90%, and the time is 48h. The drying temperature is 70℃, relative humidity is ≤10%, and the time is 48h.

[0028] In step (4), there are 5 positive plates and 6 negative plates, each with a capacity of 100Ah. The positive and negative plates are cast and welded using lead-antimony alloy (Pb-Sb2%) at a welding temperature of 430~560℃. The positive and negative plates are covered with AGM (superfine glass wool) separators in an S-shape (the negative plate is covered first, and then the positive plate is covered).

[0029] After closing the exhaust valve in step (5), maintain the pressure range of 10kPa to 25kPa.

[0030] After closing the exhaust valve in step (5), an internal formation process is adopted, charging at a current of (0.1~0.2)C for 48 hours, followed by charging at a current of (0.05~0.1)C for 24 hours. During this period, the electrolyte temperature is controlled to not exceed 50℃ for internal formation. The electrolyte has an apparent density of 1.100~1.400 g / cm³. 3 A sulfuric acid solution at a temperature of 20~30℃ is used to obtain a power-type lead-acid battery.

[0031] The preferred basic optimization scheme of this invention is adapted to conventional power scenarios:

[0032] The positive grid of the battery is cast from a nine-element alloy of lead, antimony, arsenic, tin, selenium, copper, lanthanum, aluminum and silicon. The positive grid structure adopts a plate design, with the upper half being thicker than the lower half. The vertical and horizontal ribs of the positive grid structure are elliptical, and a frame is provided on the outside. The separator encapsulates the positive electrode, and the separator has an S-shaped structure.

[0033] Further, the upper half of the positive grid has a thickness of 3-5 mm, and the lower half has a thickness of 2-3 mm; the nine-element alloy, by mass percentage, contains antimony 0.5-0.7%, arsenic 0.05-0.10%, tin 0.05-0.10%, selenium 0.02-0.03%, copper 0.03-0.035%, lanthanum 0.01-0.015%, aluminum 0.01-0.02%, silicon 0.01-0.02%, with lead as the balance.

[0034] Furthermore, the vertical ribs of the positive plate grid structure have elliptical cylinders with a minor axis of 3~5mm and a major axis of 4.5~7.5mm, and the horizontal ribs have elliptical cylinders with a minor axis of 1.5~2.5mm and a major axis of 3~4.5mm, forming a grid structure with an outer frame of 3~5mm thickness.

[0035] Furthermore, the separator is an S-shaped AGM separator with a thickness of 0.8~1.2mm, a porosity of 65%~70%, and an average pore size of 0.1~0.3μm; the plate grid has alternating openings on both sides of the electrode edge, a fully open bottom, and a semi-open upper part of the electrode plate. The S-shaped structure covers the positive electrode plate, the negative electrode plate, and the plate lugs, and first covers the negative electrode group, and then covers the positive electrode group.

[0036] Furthermore, the positive grid is provided with a plate ear on the top, and the plate ear and the positive grid are integrally cast structures; the battery is equipped with an ABS explosion-proof battery case, the battery case and the battery cover are sealed by heat fusion, a sealing ring is press-fitted at the terminal position, and an exhaust valve is provided on the top, with an exhaust valve pressure range of 10kPa~15kPa.

[0037] A further preferred technical solution of the present invention, a performance enhancement solution, is adapted to high-frequency cycling scenarios:

[0038] The positive grid of the battery is cast from a nine-element alloy of lead, antimony, arsenic, tin, selenium, copper, lanthanum, aluminum and silicon. The positive grid structure adopts a plate design, with the upper half being thicker than the lower half. The vertical ribs of the positive grid structure are elliptical and the horizontal ribs are semi-elliptical, with a frame on the outside. The separator encloses the positive electrode and has an S-shaped structure.

[0039] Furthermore, the upper half of the positive grid has a thickness of 5-8 mm, and the lower half has a thickness of 3-5 mm; the nine-element alloy, by mass percentage, contains antimony 0.7-0.9%, arsenic 0.10-0.15%, tin 0.10-0.15%, selenium 0.03-0.035%, copper 0.035-0.04%, lanthanum 0.015-0.02%, aluminum 0.02-0.025%, silicon 0.02-0.025%, with lead as the balance.

[0040] Furthermore, the vertical ribs of the positive plate grid structure have elliptical cylinders with a minor axis of 5-8 mm and a major axis of 7.5-12 mm, and the horizontal ribs have semi-elliptical cylinders with a minor axis of 2.5-4 mm and a major axis of 4.5-8 mm, forming a grid structure with an outer frame of 5-8 mm thickness; the connection between the vertical and horizontal ribs is rounded to reduce stress concentration.

[0041] Furthermore, the separator is an S-shaped AGM separator with a thickness of 1.2~1.6mm, a porosity of 70%~80%, and an average pore size of 0.3~0.7μm; the grid has fully open edges on both sides, fully open bottom, and semi-open upper part of the electrode plate; the S-shaped structure covers the positive electrode plate, negative electrode plate, and plate lugs, and first covers the negative electrode group, then covers the positive electrode group; and an auxiliary sealing strip is added to the side.

[0042] Furthermore, each grid plate has a lug, which is integrally cast with the grid plate, and the surface of the lug is passivated. The battery is equipped with an ABS explosion-proof battery case, and the battery case and battery cover are sealed with a double seal of hot melt seal and sealant. A double-layer sealing ring is press-fitted at the terminal position, and a two-way exhaust valve is provided at the top, with an exhaust valve pressure range of 15kPa~20kPa.

[0043] The preferred technical solution of this invention, the third one, is a highly corrosion-resistant solution, suitable for harsh environmental scenarios:

[0044] The positive grid of the battery is cast from a nine-element alloy of lead, antimony, arsenic, tin, selenium, copper, lanthanum, aluminum, and silicon, and the alloy surface is passivated. The positive grid structure adopts a plate design, with the upper half being thicker than the lower half. The vertical and horizontal ribs of the positive grid structure are elliptical, and a reinforcing frame is provided on the outside. The positive electrode is encapsulated by a separator, which is an S-shaped composite AGM separator (AGM material with graphene modifier added). The encapsulation method is a combination of S-shaped structure encapsulation and top semi-encapsulation.

[0045] Furthermore, the upper half of the positive grid has a thickness of 8-10 mm, and the lower half has a thickness of 5-7 mm; the nine-element alloy, by mass percentage, contains antimony 0.9-1.0%, arsenic 0.15-0.20%, tin 0.15-0.20%, selenium 0.035-0.04%, copper 0.04%, lanthanum 0.02%, aluminum 0.025-0.03%, silicon 0.025-0.03%, with lead as the balance.

[0046] Furthermore, the vertical ribs of the positive plate grid structure have elliptical cylinders with a minor axis of 8-10 mm and a major axis of 12-15 mm, and the horizontal ribs have elliptical cylinders with a minor axis of 4-5 mm and a major axis of 8-10 mm, forming a grid structure. A reinforcing frame is provided on the outside, with a frame thickness of 8-10 mm. The vertical ribs are evenly spaced, and the horizontal ribs are gradually spaced denser from top to bottom.

[0047] Furthermore, the S-shaped composite AGM separator has a thickness of 1.6~2.0mm, a porosity of 80%~85%, and an average pore size of 0.7~1.0μm; the grid has alternating openings on both sides of the electrode edge, a full opening at the bottom, and a full opening at the top of the electrode; the S-shaped structure covers the positive electrode, negative electrode, and plate lugs, and first covers the negative electrode group, then covers the positive electrode group; and an anti-corrosion coating is added to the top.

[0048] Furthermore, the top of the positive grid is provided with a plate ear, which is an integral casting structure with the positive grid. The connection between the plate ear and the busbar is reinforced by welding. The battery is equipped with a flame-retardant ABS explosion-proof battery case. The battery case and the battery cover are sealed by heat fusion. A corrosion-resistant sealing ring is press-fitted at the terminal position. An explosion-proof exhaust valve is provided at the top. The pressure range of the exhaust valve is 20kPa~25kPa. A filter device is added to the exhaust port.

[0049] The preferred technical solution of this invention, the fourth one, is a lightweight optimization solution, suitable for portable power scenarios:

[0050] The positive grid of the battery is cast from a nine-element alloy of lead, antimony, arsenic, tin, selenium, copper, lanthanum, aluminum, and silicon, with a lightweight modifier added (0.01-0.02% by mass). The positive grid structure adopts a plate design, with the upper half being thicker than the lower half. The vertical and horizontal ribs of the positive grid structure are thin elliptical, and a thin frame is provided on the outside. The separator encapsulates the positive electrode and is a thin S-shaped AGM separator.

[0051] Further, the upper half of the positive grid has a thickness of 3-4 mm, and the lower half has a thickness of 2-2.5 mm; the nine-element alloy, by mass percentage, contains antimony 0.5-0.6%, arsenic 0.05-0.08%, tin 0.05-0.08%, selenium 0.02-0.025%, copper 0.03-0.032%, lanthanum 0.01-0.012%, aluminum 0.01-0.015%, silicon 0.01-0.015%, with lead as the balance.

[0052] Furthermore, the vertical ribs of the positive grid structure have elliptical cylinders with a minor axis of 3-4 mm and a major axis of 4.5-6 mm, and the horizontal ribs have elliptical cylinders with a minor axis of 1.5-2 mm and a major axis of 3-3.5 mm, forming a grid structure. A thin frame with a thickness of 3-4 mm is provided on the outside. The entire grid is subjected to lightweight polishing treatment to remove redundant materials.

[0053] Furthermore, the thin S-shaped AGM separator has a thickness of 0.8~1.0mm, a porosity of 65%~75%, and an average pore size of 0.1~0.4μm; the grid has alternating openings on both sides of the electrode edge, a fully open bottom, and a semi-open upper part of the electrode plate. The S-shaped structure tightly covers the positive electrode plate, the negative electrode plate, and the plate lugs, and first covers the negative electrode group, then covers the positive electrode group, reducing the redundant amount of separator.

[0054] Furthermore, a small lug is provided on the top of the positive grid, and the lug and the positive grid are integrally cast structures; the battery is equipped with a lightweight ABS explosion-proof battery case, the thickness of which is optimized to 1.5~2.0mm, the battery case and the battery cover are sealed by heat fusion, a small sealing ring is press-fitted at the terminal position, and a small exhaust valve is provided on the top, with an exhaust valve pressure range of 10kPa~17kPa.

[0055] Compared with the prior art, the beneficial effects of the present invention are:

[0056] (1) The present invention significantly improves the corrosion resistance of the positive grid by using a nine-element alloy and combining it with an elliptical lead bar design. The corrosion resistance is increased by 67%~100%, effectively delaying the battery life decay caused by grid corrosion and fracture.

[0057] (2) The present invention adopts an S-shaped separator encapsulation method, which completely eliminates the short circuit phenomenon of lead wool and improves the safety and reliability of the battery during use.

[0058] (3) Through optimized electrode group casting and welding process and structural design, this invention significantly improves the cycle durability of the battery while controlling manufacturing costs. The actual number of cycles can reach more than 1050, which meets the long life requirements of power batteries. Attached Figure Description

[0059] Figure 1 This is a front view schematic diagram of the positive grid of the long-life valve-regulated explosion-proof power lead-acid battery of the present invention.

[0060] Figure 2 This is a top view of the positive plate grid of the present invention;

[0061] Figure 3 This is a left-side schematic diagram of the positive plate grid of the present invention;

[0062] Figure 4 This is a top view of the pole group of the present invention (schematic diagram of AGM partition S-shaped covering).

[0063] Figure 5 The diagram shows the main view of the busbar (left a is a schematic diagram of the prior art partition covering, right b is a schematic diagram of the partition covering the bottom of the busbar of the present invention).

[0064] In the diagram: 1. Lug; 2. Vertical rib; 3. Horizontal rib; 4. Frame; 5. Partition; 6. Positive electrode plate; 7. Negative electrode plate. Detailed Implementation

[0065] The present invention will be further described below with reference to specific embodiments.

[0066] A front view schematic diagram of the positive grid of the long-life valve-regulated explosion-proof power lead-acid battery of the present invention, as shown below. Figure 1 As shown, it includes: a top lug 1 for welding to the electrode post to achieve current collection and conduction; longitudinally distributed elliptical vertical ribs 2, together with transverse horizontal ribs 3 (elliptical or semi-elliptical) to form a grid structure, optimizing current distribution and mechanical strength; and an outer frame 4 to provide structural support and prevent active material from falling off the electrode edge. The positive plate grid adopts a gradient design with the upper half being thicker than the lower half to suppress corrosion and deformation under deep cycling conditions.

[0067] A top view of the positive plate grid of the present invention is shown below. Figure 2 As shown, the major axis of the vertical rib 2 (elliptical) is parallel to the plane of the grid, which increases the contact area with the active material and improves the adhesion; the frame 4 is integrally cast with the vertical and horizontal ribs to form a closed frame and enhance the grid's resistance to deformation.

[0068] A left-side view of the positive plate grid of the present invention is shown below. Figure 3 As shown, the lug 1 smoothly transitions to the main body of the grid, facilitating full wetting of the busbar during casting and welding; the side view of the horizontal rib 3 is clear, and the semi-elliptical design can reduce the weight of the grid while ensuring strength; the side view of the frame 4 shows that its thickness is uniform, and together with the horizontal and vertical ribs, it forms a three-dimensional support structure. The figure clearly shows the gradient characteristic that the upper half of the grid is thicker than the lower half.

[0069] A top view of the electrode group of the present invention (S-shaped coverage of the AGM partition), as shown below. Figure 4 As shown, the separator 5 adopts an S-shaped structure (AGM material) and alternately covers the positive electrode plate 6 and the negative electrode plate 7 to achieve an alternating opening on both sides of the electrode plate edge, a fully open bottom, and a semi-open upper part of the electrode plate. The separator first covers the negative electrode group and then covers the positive electrode group, which improves the reliability of the coating, ensuring electrolyte penetration and gas recombination, and effectively preventing micro-short circuits.

[0070] Existing technology partition covering diagram as shown Figure 5 As shown in (a), the separator only covers the edge of the electrode plate and does not extend to the bottom of the busbar, which can easily lead to the shedding of active material at the edge of the electrode plate and an increased risk of micro-short circuits; the schematic diagram of the separator covering of the present invention is shown below. Figure 5 As shown in (b), the S-shaped AGM separator covers the bottom of the busbar, achieving full wrapping of the plates and lugs, effectively blocking direct contact between the edge of the plates and the busbar, and improving the safety and lifespan of the battery under vibration and impact conditions.

[0071] Specifically, the manufacturing method of the long-life valve-regulated explosion-proof power lead-acid battery of the present invention includes the following steps:

[0072] (1) Preparation of positive grid: The positive grid is manufactured by gravity casting. The positive grid is a nine-element alloy. The specific process parameters of gravity casting are: mold temperature 100~180℃, alloy melting temperature 430~560℃, casting speed 3~6 pieces / min, water cooling 5s.

[0073] (2) Preparation of positive electrode plate: A paste-coating method is adopted, using lead powder, red lead powder, sulfuric acid, water, and polypropylene fiber to manufacture positive electrode lead paste with an apparent density of 4.2~4.6 g / cm³. 3 Apply the positive electrode lead paste to the positive plate grid, with a thickness of 4.5~6mm on the upper half and 2.5~4mm on the lower half; then cure it at 35℃, 90% relative humidity for 48h, and then dry it at 70℃, ≤10% relative humidity for 48h to obtain the positive electrode plate.

[0074] (3) Preparation of negative electrode plate: A paste-coating method is adopted, using lead powder, sulfuric acid, water, polypropylene fiber, sodium lignosulfonate, carbon black, barium sulfate, etc. to manufacture negative electrode lead paste, with an apparent density of 4.2~4.6 g / cm³. 3 The negative electrode lead paste is applied to the negative plate grid and then cured at a temperature of 35℃, a relative humidity of 90%, and a time of 48 hours. After drying, the drying temperature is 70℃, the relative humidity is ≤10%, and the time is 48 hours to obtain the negative electrode plate.

[0075] (4) Preparation of positive and negative electrode groups: The positive and negative electrode groups are combined according to the rule of alternating positive and negative electrode plates. Then, the electrode group welding and electrode column casting are completed by casting and welding technology using lead-antimony alloy. There are 5 positive electrode plates and 6 negative electrode plates, each with a capacity of 100Ah. The positive and negative electrode plates are cast and welded using lead-antimony alloy (Pb-Sb2%) at a welding temperature of 430~560℃. The positive and negative electrode plates are covered with AGM (superfine glass wool) separators in an S-shape. The negative electrode plate is covered first, and then the positive electrode plate is covered.

[0076] (5) Preparation of power-type lead-acid batteries: The positive and negative electrode groups are formed, and then placed into an ABS explosion-proof battery case. The explosion-proof battery case and cover are heat-sealed, the terminal sealing ring is pressed in, the exhaust valve is closed, and the pressure is maintained at 10 kPa~25 kPa. An internal formation process is adopted, and the battery is charged at a current of 0.1~0.2C for 48 hours, followed by charging at a current of 0.05~0.1C for 24 hours. During this period, the electrolyte temperature is controlled not to exceed 50℃ for internal formation, and the apparent density is 1.100~1.400 g / cm³. 3 A sulfuric acid solution at a temperature of 20~30℃ is used to obtain a power-type lead-acid battery.

[0077] Example 1

[0078] The long-life valve-regulated explosion-proof power lead-acid battery of the present invention has a positive grid made of a nine-element alloy of lead, antimony, arsenic, tin, selenium, copper, lanthanum, aluminum and silicon. The alloy composition by mass percentage is as follows: antimony 0.5%, arsenic 0.05%, tin 0.05%, selenium 0.02%, copper 0.03%, lanthanum 0.01%, aluminum 0.01%, silicon 0.01%, with lead as the balance.

[0079] The main plate grid structure adopts a plate design, with the upper half being 3mm thick and the lower half being 2mm thick. The vertical ribs are elliptical cylinders with a minor axis of 3mm and a major axis of 4.5mm, and the horizontal ribs are elliptical cylinders with a minor axis of 1.5mm and a major axis of 3mm. The vertical and horizontal ribs form a grid structure, and there is a frame on the outside with a frame thickness of 3mm. The top of the main plate grid is equipped with a plate ear, which is an integral casting structure with the main plate grid.

[0080] The separator is an S-shaped AGM separator with a thickness of 0.8 mm, a porosity of 65%, and an average pore size of 0.1 μm. The separator is encapsulated in an S-shaped structure with alternating openings on both sides of the electrode edge, a full opening at the bottom, and a semi-open opening at the top of the electrode. The S-shaped structure encapsulates the positive electrode, the negative electrode, and the lugs, and encapsulates the negative electrode group first, followed by the positive electrode group.

[0081] The battery is equipped with an ABS explosion-proof battery case. The battery case and battery cover are sealed by heat fusion. A sealing ring is press-fitted at the terminal position. An exhaust valve is provided at the top. The pressure range of the exhaust valve is 10kPa.

[0082] The method for manufacturing this storage battery includes the following steps:

[0083] (1) Preparation of positive grid: The positive grid is manufactured by gravity casting. The positive grid is the above-mentioned nine-element alloy. Gravity casting process parameters: mold temperature 100℃, alloy melting temperature 430℃, casting speed 3 pieces / min, water cooling 5s.

[0084] (2) Preparation of the positive electrode plate: A paste-type positive electrode lead paste was prepared according to the following mass ratio: 82 parts lead powder, 6 parts red lead powder, 5 parts 98% concentrated sulfuric acid, 7 parts deionized water, and 0.2 parts polypropylene fiber. After mixing and stirring evenly, the apparent density of the lead paste was 4.2 g / cm³. 3 Apply the positive electrode lead paste to the positive plate grid, with a thickness of 4.5 mm on the upper half and 2.5 mm on the lower half; then cure it for 48 hours at a temperature of 35℃ and a relative humidity of 90%, and then dry it for 48 hours at a temperature of 70℃ and a relative humidity of ≤10% to obtain the positive electrode plate.

[0085] (3) Preparation of negative electrode plate: The negative electrode lead paste is prepared by the following mass ratio: 85 parts lead powder, 4 parts 98% concentrated sulfuric acid, 8 parts deionized water, 0.15 parts polypropylene fiber, 0.4 parts sodium lignosulfonate, 0.6 parts carbon black, and 1.0 parts barium sulfate. After mixing and stirring evenly, the apparent density of the lead paste is 4.2 g / cm³. The negative electrode lead paste is applied to the negative plate grid and then cured for 48 h at a temperature of 35℃ and a relative humidity of 90%, and then dried for 48 h at a temperature of 70℃ and a relative humidity of ≤10% to obtain the negative electrode plate.

[0086] (4) Preparation of positive and negative electrode groups: The positive and negative electrode groups are combined according to the rule of alternating positive and negative electrode plates. There are 5 positive electrode plates and 6 negative electrode plates, each with a capacity of 100Ah. The positive and negative electrode plates are cast and welded using lead-antimony alloy (Pb-Sb2%) at a welding temperature of 430℃. The positive and negative electrode plates are covered with AGM separators in an S-shape, first covering the negative electrode plate and then covering the positive electrode plate.

[0087] (5) Preparation of power-type lead-acid batteries: The positive and negative electrode groups are formed, and then placed into an ABS explosion-proof battery case. The explosion-proof battery case and cover are heat-sealed, the terminal sealing ring is pressed in, and the exhaust valve is closed. An internal formation process is adopted, and the battery is charged at a current of 0.1C for 48 hours, followed by charging at a current of 0.05C for 24 hours. During this period, the electrolyte temperature is controlled not to exceed 50°C. The electrolyte has an apparent density of 1.100 g / cm³. 3 A sulfuric acid solution at 20°C is used to obtain a power-type lead-acid battery.

[0088] Example 2

[0089] The long-life valve-regulated explosion-proof power lead-acid battery of the present invention has a positive grid made of a nine-element alloy of lead, antimony, arsenic, tin, selenium, copper, lanthanum, aluminum and silicon. The alloy composition by mass percentage is as follows: antimony 0.8%, arsenic 0.12%, tin 0.12%, selenium 0.03%, copper 0.035%, lanthanum 0.015%, aluminum 0.02%, silicon 0.02%, with lead as the balance.

[0090] The main plate grid structure adopts a plate design, with the upper half being 6mm thick and the lower half being 4.5mm thick. The vertical ribs are elliptical cylinders with a minor axis of 6.5mm and a major axis of 9.75mm, and the horizontal ribs are elliptical cylinders with a minor axis of 3.25mm and a major axis of 6.5mm. The vertical and horizontal ribs form a grid structure, and there is a frame on the outside with a frame thickness of 6.5mm. The top of the main plate grid is equipped with a plate lug, which is an integral casting structure with the main plate grid.

[0091] The separator is an S-shaped AGM separator with a thickness of 1.4 mm, a porosity of 75%, and an average pore size of 0.55 μm. The separator is encapsulated in an S-shaped structure with alternating openings on both sides of the electrode edge, a full opening at the bottom, and a semi-open opening at the top of the electrode. The S-shaped structure covers the positive electrode, negative electrode, and plate lugs, and first covers the negative electrode group, then covers the positive electrode group.

[0092] The battery is equipped with an ABS explosion-proof battery case. The battery case and battery cover are sealed by heat fusion. A sealing ring is press-fitted at the terminal position. An exhaust valve is provided at the top. The pressure range of the exhaust valve is 17.5 kPa.

[0093] The method for manufacturing this storage battery includes the following steps:

[0094] (1) Preparation of positive grid: The positive grid is manufactured by gravity casting. The positive grid is the above-mentioned nine-element alloy. Gravity casting process parameters: mold temperature 140℃, alloy melting temperature 495℃, casting speed 4.5 pieces / min, water cooling 5s.

[0095] (2) Preparation of the positive electrode plate: A paste-type positive electrode lead paste was prepared according to the following mass ratio: 83 parts lead powder, 6.5 parts red lead powder, 5.0 parts 98% concentrated sulfuric acid, 7.0 parts deionized water, and 0.2 parts polypropylene fiber. After mixing and stirring evenly, the apparent density of the lead paste was 4.4 g / cm³. 3 Apply positive electrode lead paste to the positive plate grid, with a thickness of 5.25 mm on the upper half and 3.25 mm on the lower half; then cure it for 48 hours at a temperature of 35℃ and a relative humidity of 90%, and then dry it for 48 hours at a temperature of 70℃ and a relative humidity of ≤10% to obtain the positive electrode plate.

[0096] (3) Preparation of negative electrode plate: The negative electrode lead paste is prepared by the following mass ratio: 85 parts lead powder, 4.0 parts 98% concentrated sulfuric acid, 8.0 parts deionized water, 0.15 parts polypropylene fiber, 0.4 parts sodium lignosulfonate, 0.65 parts carbon black, and 1.0 parts barium sulfate. After mixing and stirring evenly, the apparent density of the lead paste is 4.4 g / cm³. The negative electrode lead paste is applied to the negative plate grid and then cured for 48 h at a temperature of 35℃ and a relative humidity of 90%, and then dried for 48 h at a temperature of 70℃ and a relative humidity of ≤10% to obtain the negative electrode plate.

[0097] (4) Preparation of positive and negative electrode groups: The positive and negative electrode groups are combined according to the rule of alternating positive and negative electrode plates. There are 5 positive electrode plates and 6 negative electrode plates, each with a capacity of 100Ah. The positive and negative electrode plates are cast and welded using lead-antimony alloy (Pb-Sb 2%) at a welding temperature of 495℃. The positive and negative electrode plates are covered with AGM separators in an S-shape, first covering the negative electrode plate and then covering the positive electrode plate.

[0098] (5) Preparation of power-type lead-acid batteries: The positive and negative electrode groups are formed, then placed into an ABS explosion-proof battery case, the explosion-proof battery case and cover are heat-sealed, the terminal sealing ring is pressed in, and the exhaust valve is closed; an internal formation process is adopted, charging at a current of 0.15C for 48 hours, followed by charging at a current of 0.075C for 24 hours, during which the electrolyte temperature is controlled not to exceed 50℃; the electrolyte has an apparent density of 1.250 g / cm³. 3 A sulfuric acid solution at 25°C is used to obtain a power-type lead-acid battery.

[0099] Example 3

[0100] The long-life valve-regulated explosion-proof power lead-acid battery of the present invention has a positive grid made of a nine-element alloy of lead, antimony, arsenic, tin, selenium, copper, lanthanum, aluminum and silicon. The alloy composition by mass percentage is as follows: antimony 1.0%, arsenic 0.20%, tin 0.20%, selenium 0.04%, copper 0.04%, lanthanum 0.02%, aluminum 0.03%, silicon 0.03%, with lead as the balance.

[0101] The main plate grid structure adopts a plate design, with the upper half being 10mm thick and the lower half being 7mm thick. The vertical ribs are elliptical cylinders with a minor axis of 10mm and a major axis of 15mm, and the horizontal ribs are elliptical cylinders with a minor axis of 5mm and a major axis of 10mm. The vertical and horizontal ribs form a grid structure, and there is a frame on the outside with a frame thickness of 10mm. The top of the main plate grid is equipped with a plate ear, which is an integral casting structure with the main plate grid.

[0102] The separator is an S-shaped AGM separator with a thickness of 2.0 mm, a porosity of 85%, and an average pore size of 1.0 μm. The separator is encapsulated in an S-shaped structure with alternating openings on both sides of the electrode edge, a full opening at the bottom, and a semi-open opening at the top of the electrode. The S-shaped structure covers the positive electrode, the negative electrode, and the lugs, and first covers the negative electrode group, then covers the positive electrode group.

[0103] The battery is equipped with an ABS explosion-proof battery case. The battery case and battery cover are sealed by heat fusion. A sealing ring is press-fitted at the terminal position. An exhaust valve is provided at the top. The pressure range of the exhaust valve is 25kPa.

[0104] The method for manufacturing this storage battery includes the following steps:

[0105] (1) Preparation of positive grid: The positive grid is manufactured by gravity casting. The positive grid is the above-mentioned nine-element alloy. Gravity casting process parameters: mold temperature 180℃, alloy melting temperature 560℃, casting speed 6 pieces / min, water cooling 5s.

[0106] (2) Preparation of the positive electrode plate: A paste-coating method was adopted. The positive electrode lead paste was prepared according to the following mass ratio: 84 parts lead powder, 7.5 parts red lead powder, 5.5 parts 98% concentrated sulfuric acid, 7.5 parts deionized water, and 0.25 parts polypropylene fiber. After mixing and stirring evenly, the apparent density of the lead paste was 4.6 g / cm³. 3 Apply the positive electrode lead paste to the positive plate grid, with a thickness of 6 mm on the upper half and 4 mm on the lower half; then cure it for 48 hours at a temperature of 35℃ and a relative humidity of 90%, and then dry it for 48 hours at a temperature of 70℃ and a relative humidity of ≤10% to obtain the positive electrode plate.

[0107] (3) Preparation of negative electrode plate: The negative electrode lead paste is prepared by the following mass ratio: 86 parts lead powder, 4.5 parts 98% concentrated sulfuric acid, 8.5 parts deionized water, 0.18 parts polypropylene fiber, 0.45 parts sodium lignosulfonate, 0.75 parts carbon black, and 1.1 parts barium sulfate. After mixing and stirring evenly, the apparent density of the lead paste is 4.6 g / cm³. The negative electrode lead paste is applied to the negative plate grid and then cured for 48 h at a temperature of 35℃ and a relative humidity of 90%, and then dried for 48 h at a temperature of 70℃ and a relative humidity of ≤10% to obtain the negative electrode plate.

[0108] (4) Preparation of positive and negative electrode groups: The positive and negative electrode groups are combined according to the rule of alternating positive and negative electrode plates. There are 5 positive electrode plates and 6 negative electrode plates, each with a capacity of 100Ah. The positive and negative electrode plates are cast and welded using lead-antimony alloy (Pb-Sb 2%) at a welding temperature of 560℃. The positive and negative electrode plates are covered with AGM separators in an S-shape, first covering the negative electrode plate and then covering the positive electrode plate.

[0109] (5) Preparation of power-type lead-acid batteries: The positive and negative electrode groups are formed, and then placed into an ABS explosion-proof battery case. The explosion-proof battery case and cover are heat-sealed, the terminal sealing ring is pressed in, and the exhaust valve is closed. An internal formation process is used, and the battery is charged at a current of 0.2C for 48 hours, followed by charging at a current of 0.1C for 24 hours. During this period, the electrolyte temperature is controlled to not exceed 50°C. The electrolyte has an apparent density of 1.400 g / cm³. 3 A sulfuric acid solution at 30°C is used to obtain a power-type lead-acid battery.

[0110] Comparative Example 1

[0111] A valve-regulated explosion-proof power lead-acid battery is identical in structure, manufacturing process and all parameters to that of Example 1. The only difference is that the lead rib structure of the positive grid adopts a regular tetrahedral structure (both vertical and horizontal ribs are regular tetrahedral with an edge length of 2.0 mm), instead of the elliptical structure of Example 1.

[0112] The manufacturing method of this battery is exactly the same as that of Example 1, except that when preparing the positive grid, the lead bar mold is replaced with a tetrahedral structure mold. All other process parameters (mold temperature 100℃, alloy melting temperature 430℃, etc.) are the same as those of Example 1.

[0113] Comparative Example 2

[0114] A valve-regulated explosion-proof power lead-acid battery is identical in structure, manufacturing process, and all parameters to that of Example 1, except that the positive grid does not use a nine-element alloy, but a seven-element alloy of lead-antimony-arsenic-tin-copper-selenium-lanthanum. The alloy composition by mass percentage is as follows: antimony 0.5%, arsenic 0.05%, tin 0.05%, selenium 0.02%, copper 0.03%, lanthanum 0.01%, with lead as the balance (excluding aluminum and silicon).

[0115] The manufacturing method of this battery is exactly the same as that of Example 1, except that the above-mentioned seven-element alloy is used for melting and casting when preparing the positive grid. All other process parameters are the same as those of Example 1.

[0116] Comparative Example 3

[0117] A valve-regulated explosion-proof power lead-acid battery is identical to that of Example 1 in structure, manufacturing process and all parameters. The only difference is that the thickness of the upper half and the lower half of the positive grid is the same, both being 2.5 mm. The rest of the grid structure (elliptical lead ribs, frame thickness of 3 mm, etc.) is the same as that of Example 1.

[0118] The manufacturing method of this battery is completely the same as that of Example 1, except that when preparing the positive grid, the thickness of the upper and lower halves of the grid is set to 2.5 mm, and the coating thickness of the upper and lower halves of the positive electrode lead paste is adjusted to 3.5 mm (to match the grid thickness). All other process parameters are the same as those of Example 1.

[0119] Performance testing

[0120] The valve-regulated explosion-proof power lead-acid batteries prepared in Examples 1-3 and Comparative Examples 1-3 were compared with existing conventional valve-regulated power lead-acid batteries (control group, purchased from Tianneng Group Co., Ltd., model: 6-DZM-100, specification: 12V 100Ah) in terms of performance. The test results are shown in the table below:

[0121] Table 1 Performance Parameters

[0122]

[0123] The test results above show that the long-life valve-regulated explosion-proof power lead-acid battery prepared by this invention (Examples 1-3) can achieve a cycle life of over 1050 cycles, significantly improved corrosion resistance, completely eliminates lead wool short circuits, and has excellent explosion-proof performance. Its overall performance is far superior to existing conventional products (control group) and comparative examples. Comparative Example 1 uses tetrahedral lead bars in its positive grid, which easily leads to stress concentration at the corners, accelerating the corrosion rate and resulting in a corrosion resistance improvement of only 32%, with the cycle life reduced to 720 cycles. Comparative Example 2 does not use the non-metallic alloy of this invention (lacking aluminum and silicon elements), resulting in insufficient alloy grain refinement and decreased corrosion resistance, with a cycle life of only 680 cycles. Comparative Example 3 has a uniform thickness in the upper and lower halves of its positive grid, which cannot alleviate corrosion in the high current density area in the middle and upper parts, resulting in a significant decrease in both corrosion resistance and cycle life, with a cycle life of 750 cycles. The above comparison results fully demonstrate that the nine-element alloy, the elliptical lead rib structure, and the gradient thickness design of the upper and lower grids of the present invention have a synergistic effect on improving the corrosion resistance and cycle life of the battery, and none of them can be omitted.

Claims

1. A long-life valve-regulated explosion-proof power lead-acid battery, characterized in that: The positive grid of the battery is cast from a nine-element alloy of lead, antimony, arsenic, tin, selenium, copper, lanthanum, aluminum, and silicon. The positive grid structure adopts a plate design, with the upper half being thicker than the lower half. The vertical and horizontal ribs of the positive grid are elliptical or semi-elliptical, and a frame is provided on the outside. The separator has an S-shaped structure, with alternating openings on both sides of the grid's electrode edge, a fully open bottom, and a semi-open upper part of the electrode. The S-shaped structure covers the positive and negative electrode plates. The upper half of the positive plate grid has a thickness of 3~10mm, and the lower half has a thickness of 2~7mm; The nine-element alloy of the positive grid has the following content by mass percentage: antimony 0.5~1.0, arsenic 0.05~0.20, tin 0.05~0.20, selenium 0.02~0.04, copper 0.03~0.04, lanthanum 0.01~0.02, aluminum 0.01~0.03, silicon 0.01~0.03, with lead as the balance. The vertical ribs of the positive plate grid structure have elliptical cylinders with a minor axis of 3~10mm and a major axis of 4.5~15mm, and the horizontal ribs have elliptical cylinders with a minor axis of 1.5~5mm and a major axis of 3~10mm. They are grid-like structures with a frame on the outside, and the frame thickness is 3~10mm. The partition is made of AGM material, and the S-shaped structure is also covered with lugs; The thickness of the AGM is 0.8~4.0mm, the porosity of the partition is 65%~95%, and the average pore size is ≤22μm.

2. The long-life valve-regulated explosion-proof power lead-acid battery according to claim 1, characterized in that: The top of the positive plate grid is provided with a plate lug, and the plate lug and the positive plate grid are integrally cast structures.

3. The long-life valve-regulated explosion-proof power lead-acid battery according to claim 1, characterized in that: The battery is equipped with an explosion-proof battery compartment, the battery compartment and the battery cover are sealed by heat fusion, a sealing ring is press-fitted at the terminal position, and an exhaust valve is provided at the top.

4. A method for manufacturing a long-life valve-regulated explosion-proof power lead-acid battery according to claim 1, characterized in that: Includes the following steps: (1) Preparation of positive grid: The positive grid is manufactured by gravity casting and is made of nine-element alloy; (2) Preparation of positive electrode plate: The positive electrode lead paste is applied to the positive plate grid by paste application, and then cured and dried to obtain the positive electrode plate; (3) Preparation of negative electrode plate: The negative electrode lead paste is applied to the negative plate grid by paste application, and then cured and dried to obtain the negative electrode plate; (4) Preparation of positive and negative electrode groups: The positive and negative electrode groups are combined according to the rule of alternating positive and negative electrode plates. Then, lead-antimony alloy is used to complete the electrode group welding and electrode column casting by casting and welding technology. The separator first covers the negative electrode group and then covers the positive electrode group. (5) Preparation of power type lead-acid battery: The positive electrode group and the negative electrode group are formed, and then placed into the explosion-proof battery case. The explosion-proof battery case and cover are heat-sealed, the terminal sealing ring is pressed in, and the exhaust valve is closed to obtain the power type lead-acid battery.

5. The manufacturing method of the long-life valve-regulated explosion-proof power lead-acid battery according to claim 4, characterized in that: Step (1) Specific process parameters for gravity casting: mold temperature 100~180℃, alloy melting temperature 430~560℃, casting speed 3~6 pieces / min, water cooling 5s.

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