CN116666648A - A kind of aluminum-based composite pole plate for large-capacity and long-life lead-carbon energy storage battery and preparation method thereof - Google Patents

Abstract

The invention relates to an aluminum-based composite polar plate for a high-capacity long-life lead-carbon energy storage battery and a preparation method thereof, and belongs to the technical field of energy storage batteries. The lead-carbon energy storage battery positive composite pole plate comprises a positive pole grid and positive lead plaster coated on the positive pole grid, and the lead-carbon energy storage battery negative composite pole plate comprises a negative pole grid and negative lead plaster coated on the negative pole grid; the positive grid comprises a grid type positive plate and a positive plate aluminum conductive beam, and the negative grid comprises a grid type negative plate and a negative plate aluminum conductive beam; the grid-type positive plate consists of an aluminum-based lead-cobalt-antimony rare earth/silver coated aluminum powder composite rod, and the grid-type negative plate consists of an aluminum-based lead-tin-antimony/zirconium dioxide particle composite rod; compared with the traditional lead alloy grid, the tensile strength of the aluminum-based composite polar plate grid is improved by more than 50%, the polar plate conductivity is improved by more than 30%, and the high-current discharge performance is improved.

Description

An aluminum-based composite plate for a large-capacity and long-life lead-carbon energy storage battery and its preparation method

technical field

The invention relates to an aluminum-based composite pole plate for a lead-carbon energy storage battery with large capacity and long life and a preparation method thereof, belonging to the technical field of energy storage batteries.

Background technique

Lead-carbon battery is a capacitive lead-acid battery. Activated carbon is added to the negative electrode of the lead-acid battery to solve the problem of short cycle life of traditional lead-acid batteries and can significantly improve the life of lead-acid batteries.

The lead-carbon battery is to add a certain amount of activated carbon and conductive carbon materials to the negative plate of the lead-acid battery to eliminate the problem of sulfation during the operation of the battery to the greatest extent, thereby effectively improving the service life of the battery. However, the introduction of ordinary activated carbon into the negative electrode will greatly increase the hydrogen evolution current of the negative electrode, resulting in particularly serious water consumption during battery use and eventually lead to battery failure. Therefore, whether the problem of hydrogen evolution at the negative electrode of lead-carbon batteries can be solved becomes whether lead-carbon batteries can fully replace lead. The core problem of acid batteries. The selection of the type of carbon material and the combination of lead powder and carbon material have become bottlenecks in the performance improvement and commercialization of lead-carbon batteries. Doping Pb on the surface of carbon materials is a relatively effective method for hydrogen suppression. Simple physical mixing cannot make Pb powder doped into these pore structures, so the doping depth and uniformity are poor, and the hydrogen suppression effect that can be produced is limited. .

In recent years, many new technologies for lead-acid batteries have been developed, such as new structures, corrosion-resistant lead alloy positive grids, foamed lead grids, foamed carbon grids, new negative electrode additives, super lead-acid batteries, lead-carbon batteries, bipolar Ceramic diaphragm VRLA battery, etc. For lead-based alloys for grids, after continuous modification of the alloy formula, the grid alloys have experienced from pure lead to high-antimony alloys, low-antimony alloys, and then to lead-calcium, lead-strontium, lead-tin and other antimony-free alloys to lead-silver-calcium, Transformation of multiple alloys such as lead calcium strontium. Lead-silver-calcium alloy is the alloy used in most grids at present, and it has excellent maintenance-free performance and electrochemical performance. However, due to its antimony-free effect and poor deep cycle performance, lead-silver-calcium alloys still cannot fully meet people's needs.

Contents of the invention

In view of the above-mentioned problems existing in the current electrode plates for lead-carbon energy storage batteries, the present invention provides an aluminum-based composite plate for lead-carbon energy storage batteries with large capacity and long life and its preparation method. The conductive beams are made of aluminum plates and coated rods. The lead-clad aluminum composite structure and the symmetrical S-shaped structure grid greatly reduce the weight of the battery, increase the output power, and increase the mass specific capacity of the battery; reduce the internal resistance of the battery, excellent electrical conductivity, and improve the current conductivity of the current collector , improving the distribution of current in the plate, thereby increasing the utilization of electrode active materials.

An aluminum-based composite pole plate for a lead-carbon energy storage battery with a large capacity and long life, comprising alternately arranged positive composite pole plates of the lead-carbon energy storage battery and negative composite pole plates of the lead-carbon energy storage battery, and positive composite poles of the lead-carbon energy storage battery The plate includes a positive electrode grid 1 and a positive electrode paste coated on the positive electrode grid 1, and the negative electrode composite plate of the lead-carbon energy storage battery includes a negative electrode grid 2 and a negative electrode paste coated on the negative electrode grid 2;

The positive grid 1 includes a grid-type positive plate and a positive plate aluminum conductive beam 12 arranged on the top of the grid-type positive plate, and the negative grid 2 includes a grid-type negative plate and a negative plate aluminum plate arranged on the top of the grid-type negative plate. Conductive beam 22; the grid-type positive plate is composed of aluminum-based lead-cobalt-antimony rare earth/silver-coated aluminum powder composite rod 11, and the grid-type negative plate is composed of aluminum-based lead-tin-antimony/zirconia particle composite rod 21;

The top of the positive plate aluminum conductive beam 12 is fixed with a positive pole ear 13, and the top of the negative aluminum conductive beam is fixed with a negative pole ear 23. The positive pole ear 13 is connected through the positive confluence L-shaped aluminum bar, and the negative pole ear 23 is connected through the negative confluence L-shaped aluminum bar. , the ends of the positive confluence L-shaped aluminum bar and the negative confluence L-shaped aluminum bar are provided with copper-aluminum composite conductive heads for external power lines.

The aluminum-based lead-cobalt-antimony rare earth/silver-coated aluminum powder composite rod 11 sequentially includes an aluminum or aluminum alloy rod, a Ni-Sn/rare earth composite transition layer, a lead-calcium-tin-aluminum intermediate layer and a lead-cobalt-antimony rare earth/silver Aluminum powder-coated active layer, aluminum-based lead-tin-antimony/zirconia particle composite rod 21 sequentially includes aluminum or aluminum alloy rod, Ni-TiB ₂ composite transition layer, lead-calcium-aluminum intermediate layer and lead-tin-antimony/zirconia particle composite rod 21 from inside to outside. Zirconia grain outer layer.

Preferably, the cross-section of the aluminum or aluminum alloy rod in the aluminum-based lead-cobalt-antimony rare earth/silver-coated aluminum powder composite rod 11 is a rectangular tooth shape, the tooth pattern depth is 0.1-0.3 mm, and the tooth pattern width is 0.05-0.3 mm. The diameter of the aluminum or aluminum alloy rod is 0.5-6.0mm, the thickness of the Ni-Sn/rare earth composite transition layer is 1-10μm, the thickness of the lead-calcium-tin-aluminum interlayer is 0.5-6.0mm, the activity of lead-cobalt-antimony rare earth/silver-coated aluminum powder The thickness of the layer is 0.1-1.0mm; the aluminum-based lead-tin-antimony/zirconia particle composite rod 21 has a cross-section of aluminum or aluminum alloy rods with a rectangular tooth shape, the depth of the teeth is 0.05-0.2mm, and the width of the teeth is 0.05-0.2 mm, the diameter of the aluminum or aluminum alloy rod is 0.5-4.0mm, the thickness of the Ni-TiB ₂ composite transition layer is 1-10μm, the thickness of the lead-calcium-aluminum middle layer is 0.5-4.0mm, and the thickness of the lead-tin-antimony/zirconia outer layer 0.1 ~ 0.5mm.

The rare earth in the Ni-Sn/rare earth composite transition layer in the aluminum-based lead-cobalt-antimony rare earth/silver-coated aluminum powder composite rod 11 is CeO ₂ , La ₂ O ₃ or Nd ₂ O ₃ , and the doping amount of rare earth is 0.05-0.5 wt .%; the calcium content in the lead-calcium-tin-aluminum interlayer is 0.04-0.1wt.%, the tin content is 0.1-0.6wt.%, and the aluminum content is 0.01-0.05wt.%. The activity of lead-cobalt-antimony rare earth/silver-coated aluminum powder The rare earth in the layer is Ce, Nd, Pr or La, the content of cobalt is 0.01-0.2wt.%, the content of antimony is 0.05-0.5wt.%, the content of rare earth is 0.01-0.2wt.%, and the content of silver-coated aluminum powder is 0.2-0.2wt.%. 2wt.%, the content of silver-clad aluminum powder is 5-25wt.%;

The _TiB2 doping amount of the Ni- _TiB2 composite transition layer in the aluminum-based lead-tin-antimony/zirconia particle composite rod 21 is 0.1-1wt.%, and the calcium content in the lead-calcium-aluminum interlayer is 0.05-0.12wt.%. The content of aluminum is 0.01-0.1wt.%, and the rest is lead; the content of tin in the outer layer of lead-tin-antimony/zirconia is 0.5-2.0wt.%, the content of antimony is 0.1-1wt.%, and the content of zirconia is 0.5- 5wt.%.

The grid-type positive plate includes a positive grid frame and positive symmetrical S-shaped grid ribs, and the grid-type negative plate includes a negative grid frame and negative symmetrical S-shaped grid ribs.

The aluminum conductive beam 12 on the positive plate and the aluminum conductive beam 22 on the negative plate all include an aluminum or aluminum alloy substrate, a hard anodized film layer, an anti-corrosion PTFE composite modified primer layer and a silicone metal glue anti-corrosion layer from the inside to the outside. .

Preferably, the thickness of the hard anodic oxidation film layer is 20-50 μm, the thickness of the anti-corrosion PTFE composite modified primer layer is 20-100 μm, and the thickness of the silicone-metal glue anti-corrosion layer is 40-200 μm.

The preparation method of the positive plate aluminum conductive beam, the specific steps are as follows:

(1) The aluminum conductive beam is sequentially washed with NaOH solution to remove oil and deionized water to obtain a pretreated aluminum conductive beam;

(2) Place the pretreated aluminum conductive beam in a modified sulfuric acid solution for hard anodic oxidation, wash it with deionized water, seal it in hot water, dry it, and then heat it in a vacuum at a temperature of 400-600°C for 0.5 ~2h to obtain a hard anodized film layer;

(3) immerse the aluminum conductive beam coated with a hard anodic oxidation film layer in a modified PTFE emulsion with a temperature of 60-120° C. and coat it for 2-10 minutes to obtain an anti-corrosion PTFE composite modified primer layer;

(4) At a temperature of 70-120° C., apply commercially available silicone-on-metal glue on the surface of an aluminum conductive beam coated with an anti-corrosion PTFE composite modified primer layer and cure for 1-3 hours to obtain a silicone-on-metal glue anti-corrosion layer.

The modified sulfuric acid solution contains sulfuric acid 200-300g/L, glycerin 16-30ml/L, oxalic acid 10-30g/L, aluminum sulfate 10-30g/L; the temperature of hard anodic oxidation is 0.5-5°C, the current The density is 0.5~4A/dm ² , the cell voltage is 30~60V, the air is blown and stirred at the bottom, and the oxidation time is 1~4h.

Based on the mass of positive electrode paste as 100%, lead powder 75-90%, hollow glass microspheres/MnO ₂ 1.0-4.0%, tetrabasic lead sulfate powder 1.0-2.0%, colloidal graphite 0.1-0.8%, short fiber 0.1-0.2%, silicon dioxide 0.5-1.5%, sulfuric acid solution 6.0-11.5%, H ₂ O 9.0-13.0%; based on the mass of negative electrode paste as 100%, lead powder 75-85%, colloidal graphite

0.2～1.0%, modified carbon material composite powder 0.5～5.0%, superfine barium sulfate 0.3～1.0%, lignin 0.1～0.5%, short fiber 0.1～0.2%, sulfuric acid solution 6.0～9.0%, H ₂ O 9 ~ 14%; the thickness of the positive electrode paste layer is 5 ~ 9mm, and the thickness of the negative electrode paste layer is 4 ~ 7mm.

Preferably, the content of MnO ₂ in the hollow glass microspheres/MnO ₂ is 10-20wt.%;

Described hollow glass microsphere/ _MnO The preparation method, concrete steps are as follows:

(1) performing surface roughening, sensitization, and activation treatment on the hollow glass microspheres in sequence to obtain activated hollow glass microspheres;

(2) Soak activated hollow glass microspheres in Mn(NO ₃ ) ₂ -dehydrated ethanol solution for 5-20 minutes, then sinter at a temperature of 100-400°C for 10-30 minutes; repeat soaking and sintering 4-8 times, Active hollow glass microspheres/MnO ₂ are obtained.

The modified carbon material composite powder is the coconut shell activated carbon chemically plated lead-tin alloy, the lead content in the coconut shell activated carbon chemically plated lead-tin alloy is 10-20wt.%, and the tin content is 10-20wt.%.

The preparation method of described coconut shell activated carbon electroless lead-tin alloy plating, concrete steps are as follows:

(1) coarsening, sensitizing and activating the coconut shell activated carbon to obtain activated coconut shell activated carbon;

(2) Activated coconut shell activated carbon is placed in neutral electroless lead-tin alloy plating solution, and electroless plated at a temperature of 60-80° C. for 1-3 hours to obtain coconut shell activated carbon electroless lead-tin alloy plating.

The neutral electroless lead-tin alloy plating solution contains PbC1 ₂ 10-30g/L, SnC1 ₂ 10-30g/L, EDTA 10-40g/L, trisodium citrate 60-100g/L, nitrilotriacetic acid 10 ～40g/L, TiC1 ₃ (50%) 10～40mL/L; the pH value of the neutral electroless lead-tin alloy plating solution is 5～8.

The preparation method of the aluminum-based composite pole plate for the lead-carbon energy storage battery with large capacity and long life, the specific steps are as follows:

S1. Preparation of positive grid

a. Preparation of Ni-Sn/rare earth composite transition layer: Alkaline washing, deionized water washing, ultrasonic cleaning, primary zinc immersion, deionized water washing, nitric acid activation, deionized water washing, secondary zinc immersion, Electroless composite Ni-Sn/rare earth plating, deionized water washing, drying to obtain Ni-Sn/rare earth composite transition layer composite rod;

b. Preparation of the lead-calcium-tin-aluminum intermediate layer: the Ni-Sn/rare earth composite transition layer composite rod is heat-treated at a temperature of 120-300 °C for 5-10 minutes, placed in a drawing and coating extruder, and the semi-molten state Lead-calcium-tin-aluminum alloy is coated on the surface of the Ni-Sn/rare earth composite transition layer composite rod to obtain an aluminum-based/lead-calcium-tin-aluminum composite rod;

c. Aluminum-based/lead-calcium-tin-aluminum composite rods are bent to form a positive grid frame and positive symmetrical S-shaped grid ribs, and the positive grid frame and positive symmetrical S-shaped grid ribs are welded to form a grid-shaped positive plate; The specific method is: after the aluminum base/lead-calcium-tin-aluminum composite rod is calibrated in size, take the calibrated point as the apex of the arc, and bend it twice according to R=20~30mm to form the frame of the positive grid. Right angle; calibrate the length according to the distance between the bending points of the aluminum base/lead-calcium-tin-aluminum composite rod 20-60mm, and use the calibrated point as the arc on the two-dimensional plane to lay the bend according to R=8-30mm, forward and reverse alternately, round The angle between the straight rods at both ends of the arc is 105-130°, and the contact position between the bending rod and the bottom of the frame is calibrated according to the bending point distance of 50-80mm, and the calibration point is set as the arc apex with a radius R=10-40mm. arc;

d. Weld the positive aluminum conductive beam to the top of the grid-type positive plate, and place it in methanesulfonic acid solution A to electroplate the lead-cobalt-antimony rare earth/silver-coated aluminum powder composite layer to obtain the positive grid;

e. Coating the positive lead paste on the positive grid, curing and drying to obtain the positive composite plate of the lead-carbon energy storage battery;

S2. Preparation of Negative Grid

a. Preparation of Ni-TiB ₂ composite transition layer: Alkaline washing, deionized water washing, ultrasonic cleaning, primary zinc immersion, deionized water washing, nitric acid activation, deionized water washing, secondary zinc immersion, chemical Composite plating of Ni-TiB ₂ , washing with deionized water, and drying to obtain a Ni-TiB ₂ composite transition layer composite rod;

b. Preparation of the lead-calcium-aluminum intermediate layer: heat-treat the Ni-TiB ₂ composite transition layer composite rod at a temperature of 120-300°C for 5-10 minutes, place it in a drawing and coating extruder, and put the semi-molten lead-calcium Aluminum alloy is coated on the surface of the Ni-TiB ₂ composite transition layer composite rod to obtain an aluminum-based/lead-calcium-aluminum composite rod;

c. Aluminum-based/lead-calcium-aluminum composite rods are bent to form a negative grid frame and negative symmetrical S-shaped grid ribs, and the negative grid frame and negative symmetrical S-shaped grid ribs are welded to form a grid-shaped negative plate; The method is: after the aluminum-based/lead-calcium-aluminum composite rod is calibrated in size, take the calibrated point as the apex of the arc, bend it twice according to R=20-30mm to form the frame of the negative grid, and the straight rods at both ends of the arc form a right angle; According to the calibrated length of the aluminum base/lead-calcium-aluminum composite rod with a bending point spacing of 20-60mm, the calibrated point is used as an arc on the two-dimensional plane to be bent according to R=8-30mm, forward and reverse alternately, and the two ends of the arc The angle between the straight rods is 105-130°, and the contact position between the bending rod and the bottom of the frame is calibrated according to the bending point spacing of 50-80mm, and the calibration point is set as the arc apex with a radius R=10-40mm;

d. Weld the negative aluminum conductive beam to the top of the grid-type negative plate, and place it in methanesulfonic acid solution B to electroplate the lead-tin-antimony/zirconia composite layer to obtain the negative grid;

e. Coating the negative electrode lead paste on the negative electrode grid, curing and drying to obtain the negative electrode composite plate of the lead-carbon energy storage battery.

The zinc dipping solution contains NaOH 200-400g/L, ZnO 50-100g/L, potassium sodium tartrate 5-20g/L, the zinc dipping temperature is 20-40°C, and the time is 30-100s;

The electroless composite Ni-Sn/rare earth plating solution contains NiSO ₄ 7H ₂ O 25-45g/L, SnCl ₄ 5-15g/L, NaHPO ₂ 10-30g/L, sodium acetate 10-30g/L , glacial acetic acid 1~10ml/L, rare earth 1~10g/L, pH value of the plating solution is 4.4~5.0, temperature of chemical composite Ni-Sn/rare earth plating is 80~95℃, pulling speed 2-8m/min;

The methanesulfonic acid solution A contains 80-200 g/L of lead methanesulfonate, 8-24 g/L of cobalt methanesulfonate, 4-12 g/L of antimony potassium tartrate, and 4-20 g/L of nanometer CeO ₂ , Silver-coated aluminum powder 2-10g/L; the anode of the electroplated lead-cobalt-antimony rare earth/silver-coated aluminum powder composite layer is cast pure lead plate, the temperature is 30-60°C, the current density is 0.5-4A/dm ² , and the time is 1 ~6h;

The electroless composite Ni-TiB ₂ plating solution contains NiSO ₄ 7H ₂ O 40-100g/L, hydrazine hydrate 10-30g/L, sodium acetate 10-30g/L, nano-TiB ₂ 2-12g/L , the pH value of the plating solution is 9~10, the temperature of the chemical composite Ni-TiB ₂ plating is 80~95°C, and the pulling speed is 2~8m/min;

The methanesulfonic acid solution B contains 40-120 g/L of lead methanesulfonate, 10-30 g/L of stannous methanesulfonate, 2-8 g/L of antimony potassium tartrate, and 4-20 g/L of nanometer ZrO ₂ , o-chlorobenzaldehyde 0.1～0.5g/L; the anode of electroplated lead-tin-antimony/zirconia composite layer is cast pure lead plate, the temperature is 30～60℃, the current density is 0.5～4A/dm ² , and the time is 1 ~6h.

The beneficial effects of the present invention are:

(1) The positive composite polar plate of the lead-carbon energy storage battery and the negative composite polar plate of the lead-carbon energy storage battery of the present invention have strong anti-deformation and creep resistance capabilities. Compared with the traditional lead alloy grid, the tensile strength is increased by 50%. The conductivity is increased by 30%, the high-current discharge performance is improved, and the amount of heavy metal lead is reduced by more than 40%;

(2) Compared with lead alloys, aluminum is light in weight, has excellent electrical conductivity, and is light in weight. However, aluminum and its alloys are relatively active. When used directly as a conductive beam, it is easy to react with acid mist sulfuric acid to produce sulfate crystals. The cathode and anode are easily short-circuited; the hard anodic oxidation of the aluminum conductive beam in the present invention improves the strength and corrosion resistance of the aluminum and increases the surface porosity, which is beneficial to the subsequent surface coating treatment, and adopts corrosion-resistant polytetrafluoroethylene and silica gel adhesive The double-layer protection of metal glue makes the surface of the aluminum beam well protected, and will not produce a large amount of aluminum sulfate crystal salt due to the exposure of aluminum during the electrolysis process;

(3) The production of the positive and negative electrode composite rods of the present invention can adopt fully automated flow operation, which has a high degree of mechanization, can save labor costs, improve efficiency, and has a high degree of standardization, which makes the grids produced have good consistency, thereby ensuring positive and negative electrodes. The consistency of charging and discharging in use improves the current efficiency;

(4) The present invention adopts the relatively hard Ni-Sn-rare earth and Ni-TiB ₂ composite coatings with high heat resistance on the surface of aluminum rods to improve the compactness of the coatings and provide softer lead alloys for subsequent extrusion and drawing Provide support to make the composite compact and firm, and the prepared composite rod has good stability;

(5) the present invention utilizes the good electrocatalytic activity of cobalt, the electrical conductivity and the catalytic activity of silver-clad aluminum, prepare lead cobalt antimony rare earth/silver-clad aluminum powder composite coating by composite electrodeposition in methanesulfonate, greatly improve Improve the conductivity and discharge capacity of the positive electrode;

(6) the present invention adds hollow glass microspheres/ _MnO with catalytic activity in the positive lead paste Composite particles help to improve the discharge current of the battery; Add coconut shell activated carbon to coat the lead-tin alloy coating in the negative lead paste, both The problem of sulfation during battery operation is eliminated, and the problem of hydrogen evolution of activated carbon is solved.

Description of drawings

The structural schematic diagram of Fig. 1 positive electrode grid;

Figure 2 is a schematic diagram of the structure of the negative electrode grid;

Fig. 3 is a schematic diagram of the cross-sectional structure of the composite rod in Fig. 1;

Fig. 4 is a schematic diagram of the cross-sectional structure of the composite rod in Fig. 2;

Fig. 5 is a schematic diagram of the cross-sectional structure of the positive electrode conductive beam in Fig. 1;

Fig. 6 is a schematic diagram of the cross-sectional structure of the negative electrode conductive beam in Fig. 2;

In the figure: 1-positive electrode grid, 2-negative electrode grid, 11-aluminum-based lead-cobalt-antimony rare earth/silver-coated aluminum powder composite rod; 12-aluminum conductive beam of positive plate; 13-positive ear; 21-aluminum-based lead-tin Antimony/zirconia particle composite rod; 22- negative plate aluminum conductive beam; 23- negative tab; 111- positive aluminum or aluminum alloy composite rod; 112- Ni-Sn/rare earth composite transition layer; 113- lead calcium tin aluminum intermediate layer; 114-lead-cobalt-antimony rare earth/silver-coated aluminum powder active layer; 211-negative aluminum or aluminum alloy composite rod; 212-Ni-TiB ₂ composite transition layer; 213-lead-calcium-aluminum intermediate layer; Outer layer of zirconia particles; 121-aluminum base of positive conductive beam; 122-hard anodized film layer of positive conductive beam; 123-anti-corrosion PTFE composite modified primer layer of positive conductive beam; 124-silica gel sticky metal glue of positive conductive beam Anti-corrosion layer; 221-aluminum base of negative conductive beam; 222-hard anodized film layer of negative conductive beam; 223-anti-corrosion PTFE composite modified primer layer of negative conductive beam; 224-silica gel and metal glue anti-corrosion layer of negative conductive beam.

Detailed ways

The present invention will be described in further detail below in conjunction with specific embodiments, but the protection scope of the present invention is not limited to the content described.

SUMMARY OF THE INVENTION

An aluminum-based composite pole plate for a lead-carbon energy storage battery with a large capacity and long life, comprising alternately arranged positive composite pole plates of the lead-carbon energy storage battery and negative composite pole plates of the lead-carbon energy storage battery, and positive composite poles of the lead-carbon energy storage battery The plate includes a positive electrode grid 1 and a positive electrode paste coated on the positive electrode grid 1, and the negative electrode composite plate of the lead-carbon energy storage battery includes a negative electrode grid 2 and a negative electrode paste coated on the negative electrode grid 2;

The positive grid 1 includes a grid-type positive plate and a positive plate aluminum conductive beam 12 (see FIG. 1 ) that is arranged on the top of the grid-type positive plate. The negative plate aluminum conductive beam 22 at the top (see Fig. 2); the grid-type positive plate is made up of aluminum-based lead-cobalt-antimony rare earth/silver-coated aluminum powder composite rod 11, and the grid-type negative plate is made of aluminum-based lead-tin-antimony/ Composition of zirconia particle composite rod 21;

The top of the positive plate aluminum conductive beam 12 is fixed with a positive pole ear 13, and the top of the negative aluminum conductive beam is fixed with a negative pole ear 23. The positive pole ear 13 is connected through the positive confluence L-shaped aluminum bar, and the negative pole ear 23 is connected through the negative confluence L-shaped aluminum bar. , the ends of the positive confluence L-shaped aluminum bar and the negative confluence L-shaped aluminum bar are equipped with copper-aluminum composite conductive heads for external power lines;

The aluminum-based lead-cobalt-antimony rare earth/silver-coated aluminum powder composite rod 11 sequentially includes an aluminum or aluminum alloy rod, a Ni-Sn/rare earth composite transition layer, a lead-calcium-tin-aluminum intermediate layer and a lead-cobalt-antimony rare earth/silver The aluminum powder-coated active layer (see Figure 3), the aluminum-based lead-tin-antimony/zirconia particle composite rod 21 sequentially includes an aluminum or aluminum alloy rod, a Ni-TiB ₂ composite transition layer, a lead-calcium-aluminum intermediate layer and The outer layer of lead-tin-antimony/zirconia particles (see Figure 4);

The grid-type positive plate includes a positive grid frame and a positive symmetrical S-shaped grid rib, and the grid-type negative plate includes a negative grid frame and a negative symmetrical S-shaped grid rib;

The aluminum conductive beam 12 on the positive plate and the aluminum conductive beam 22 on the negative plate all include an aluminum or aluminum alloy substrate, a hard anodized film layer, an anti-corrosion PTFE composite modified primer layer and a silicone metal glue anti-corrosion layer from the inside to the outside. ;

The positive electrode composite plate of the lead-carbon energy storage battery and the negative electrode composite plate of the lead-carbon energy storage battery have strong resistance to deformation and creep. Compared with the traditional lead alloy grid, the tensile strength is increased by 50%, and the conductivity of the plate is increased by 30%. , High-current discharge performance is improved, and the amount of heavy metal lead is reduced by more than 40%.

Embodiment 1: An aluminum-based composite pole plate (see Figure 1-6) for a lead-carbon energy storage battery with a large capacity and long life, comprising alternately arranged lead-carbon energy storage battery positive composite pole plates and lead-carbon energy storage battery negative electrode composites Pole plate, the positive composite pole plate of lead-carbon energy storage battery includes positive pole grid 1 and the positive electrode paste coated on the positive pole grid 1, the negative pole composite pole plate of lead-carbon energy storage battery includes negative pole grid 2 and coating setting Negative lead paste on the negative grid 2;

The positive grid 1 includes a grid-type positive plate and a positive plate aluminum conductive beam 12 arranged on the top of the grid-type positive plate, and the negative grid 2 includes a grid-type negative plate and a negative plate aluminum plate arranged on the top of the grid-type negative plate. Conductive beam 22; the grid-type positive plate is composed of aluminum-based lead-cobalt-antimony rare earth/silver-coated aluminum powder composite rod 11, and the grid-type negative plate is composed of aluminum-based lead-tin-antimony/zirconia particle composite rod 21;

The top of the positive plate aluminum conductive beam 12 is fixed with a positive pole ear 13, and the top of the negative aluminum conductive beam is fixed with a negative pole ear 23. The positive pole ear 13 is connected through the positive confluence L-shaped aluminum bar, and the negative pole ear 23 is connected through the negative confluence L-shaped aluminum bar. , the ends of the positive confluence L-shaped aluminum bar and the negative confluence L-shaped aluminum bar are equipped with copper-aluminum composite conductive heads for external power lines;

Aluminum-based lead-cobalt-antimony rare earth/silver-coated aluminum powder composite rod 11 includes aluminum rod, Ni-Sn/rare earth composite transition layer, lead-calcium-tin-aluminum intermediate layer and lead-cobalt-antimony rare earth/silver-coated aluminum powder active layer from inside to outside , the aluminum-based lead-tin-antimony/zirconia particle composite rod 21 sequentially includes an aluminum rod, a Ni-TiB ₂ composite transition layer, a lead-calcium-aluminum intermediate layer and an outer layer of lead-tin-antimony/zirconia particle from the inside to the outside; Lead cobalt antimony rare earth/silver clad aluminum powder composite rod 11. The cross section of the aluminum rod is a rectangular tooth shape. The thickness of the layer is 5 μm, the thickness of the lead-calcium-tin-aluminum intermediate layer is 3.0mm, the thickness of the active layer of lead-cobalt-antimony rare earth/silver-coated aluminum powder is 0.5mm; The cross-section is a rectangular tooth shape, the depth of the tooth pattern is 0.1mm, the tooth pattern width is 0.1mm, the diameter of the aluminum rod is 2.5mm, the thickness of the Ni-TiB ₂ composite transition layer is 5μm, the thickness of the lead-calcium-aluminum intermediate layer is 2.0mm, and the lead The thickness of the outer layer of tin antimony/zirconia is 0.3mm;

The rare earth in the Ni-Sn/rare earth composite transition layer in the aluminum-based lead-cobalt-antimony rare earth/silver-coated aluminum powder composite rod 11 is _La2O3 , and the doping amount of rare earth is _0.3wt .%. In the lead-calcium-tin-aluminum interlayer The content of calcium is 0.065wt.%, the content of tin is 0.4wt.%, and the content of aluminum is 0.025wt.%. The rare earth in the active layer of lead-cobalt-antimony rare earth/silver-coated aluminum powder is Ce, the content of cobalt is 0.1wt.%, and the content of antimony 0.3wt.%, the rare earth content is 0.1wt.%, the silver-coated aluminum powder content is 1.2wt.%, and the silver-coated aluminum powder silver content is 20wt.%.

The _TiB2 doping amount of the Ni- _TiB2 composite transition layer in the aluminum-based lead-tin-antimony/zirconia particle composite rod 21 is 0.5wt.%, the calcium content in the lead-calcium-aluminum interlayer is 0.08wt.%, and the aluminum content is 0.05wt.%, the rest is lead; the content of tin in the outer layer of lead-tin-antimony/zirconia is 1.0wt.%, the content of antimony is 0.5wt.%, and the content of zirconia is 2.5wt.%.

The grid-type positive plate includes a positive grid frame and a positive symmetrical S-shaped grid rib, and the grid-type negative plate includes a negative grid frame and a negative symmetrical S-shaped grid rib;

The positive plate aluminum conductive beam 12 (see FIG. 5 ) and the negative plate aluminum conductive beam 22 (see FIG. 6 ) all sequentially include an aluminum substrate, a hard anodized film layer, and an anti-corrosion PTFE composite modified primer layer from the inside to the outside. And silicone metal glue anti-corrosion layer; the thickness of the positive aluminum conductive beam is 12mm, and the thickness of the negative aluminum conductive beam is 10mm;

The thickness of the hard anodized film layer is 35 μm, the thickness of the anti-corrosion PTFE composite modified primer layer is 60 μm, and the thickness of the silicone metal glue anti-corrosion layer is 100 μm;

The preparation method of the positive plate aluminum conductive beam, the specific steps are as follows:

(1) The aluminum conductive beam is sequentially washed with a NaOH solution with a concentration of 15wt.% to remove oil and deionized water to obtain a pretreated aluminum conductive beam;

(2) Place the pretreated aluminum conductive beam in a modified sulfuric acid solution at a temperature of 2°C, a current density of 2A/dm ² , a cell voltage of 50V, and carry out hard anodic oxidation for 2 hours under the condition of blowing and stirring at the bottom, and deionize After washing with water, place it in hot water to seal, blow dry, and place it under vacuum heat treatment at 500°C for 1.5 hours to obtain a hard anodized film layer; the modified sulfuric acid solution contains 250g/L of sulfuric acid, 20ml/L of glycerin, and 20g of oxalic acid /L, aluminum sulfate 20g/L;

(3) immerse the aluminum conductive beam coated with the hard anodized film layer in the modified PTFE emulsion with a temperature of 90° C. and coat it for 6 minutes to obtain the anti-corrosion PTFE composite modified primer layer;

(4) At a temperature of 100°C, apply commercially available silica gel to metal glue on the surface of an aluminum conductive beam coated with an anti-corrosion PTFE composite modified primer layer and cure for 2 hours to obtain a silica gel to metal glue anti-corrosion layer;

Based on the mass of positive lead paste as 100%, lead powder 80%, hollow glass microspheres/MnO ₂ 2.0%, tetrabasic lead sulfate powder 1.5%, colloidal graphite 0.6%, short fiber 0.15%, silicon dioxide 1.0% , sulfuric acid solution 9%, H ₂ O 11%; based on the mass of negative electrode paste as 100%, lead powder 80%, colloidal graphite 0.6%, modified carbon material composite powder 2.5%, ultrafine barium sulfate 0.6%, wood 0.3% prime, 0.15% short fiber, 7.5% sulfuric acid solution, 11% _H2O ; the thickness of the positive electrode paste layer is 7mm, and the thickness of the negative electrode paste layer is 5mm;

Hollow glass microspheres/ _MnO Content of _MnO2 is 15wt.%; described hollow glass microspheres/ _{MnO2Preparation} method, concrete steps are as follows:

(1) The hollow glass microspheres are roughened with 10g/L KF, sensitized with 10g/L _SnC1 + 10ml/L hydrochloric acid, and activated with 4g/L _AgNO3 solution to obtain activated hollow glass microspheres;

(2) Soak activated hollow glass microspheres in Mn(NO ₃ ) ₂ -absolute ethanol solution with a concentration of 20wt.% for 10 minutes, and then sinter at 200°C for 20 minutes; repeat soaking and sintering 6 times to obtain activated hollow glass microspheres. Glass beads/MnO ₂ ;

The modified carbon material composite powder is coconut shell activated carbon chemically plated lead-tin alloy, and the lead content in the coconut shell activated carbon chemically plated lead-tin alloy is 15wt.%, and the tin content is 15wt.%.

The preparation method of described coconut shell activated carbon electroless lead-tin alloy plating, concrete steps are as follows:

(1) Coconut shell activated carbon is successively subjected to 10g/LKF coarsening, 10g/L SnC1 ₂ +10ml/L hydrochloric acid sensitization, and 1g/L PdC1 ₂ solution activation treatment to obtain activated coconut shell activated carbon;

(2) Activated coconut shell activated carbon is placed in the neutral chemical lead-tin alloy plating solution, and electroless plating is performed at a temperature of 70 ° C for 2 hours to obtain coconut shell activated carbon chemical lead-tin alloy plating; the neutral chemical lead-tin alloy plating solution contains PbCl ₂ 20g/L, SnCl ₂ 20g/L, EDTA 25g/L, trisodium citrate 80g/L, nitrilotriacetic acid 25g/L, TiC1 ₃ (50%) 25mL/L; The pH value is 7;

The preparation method of the aluminum-based composite pole plate for the lead-carbon energy storage battery with large capacity and long life, the specific steps are as follows:

S1. Preparation of positive grid

a. Preparation of Ni-Sn/rare earth composite transition layer: Alkali washing, deionized water washing, ultrasonic cleaning, primary zinc immersion, deionized water washing, nitric acid activation, deionized water washing, secondary zinc immersion, chemical compounding An automatic production line of Ni-Sn/rare earth plating, deionized water washing, and drying to obtain Ni-Sn/rare earth composite transition layer composite rods;

The zinc dipping solution contains NaOH 300g/L, ZnO 70g/L, potassium sodium tartrate 12g/L, the zinc dipping temperature is 30°C, and the time is 60S;

The electroless composite Ni-Sn/rare earth plating solution contains NiSO ₄ 7H ₂ O 35g/L, SnCl ₄ 10g/L, NaHPO ₂ 20g/L, sodium acetate 20g/L, glacial acetic acid 6ml/L, rare earth 5g/L, the pH value of the plating solution is 4.7, the temperature of chemical composite Ni-Sn/rare earth plating is 90°C, and the pulling speed is 6m/min;

b. Preparation of the lead-calcium-tin-aluminum intermediate layer: the Ni-Sn/rare earth composite transition layer composite rod is heat-treated at a temperature of 180°C for 7 minutes, placed in a drawing and coating extruder, and the semi-molten lead-calcium-tin-aluminum The alloy is coated on the surface of the Ni-Sn/rare earth composite transition layer composite rod to obtain an aluminum-based/lead-calcium-tin-aluminum composite rod;

c. Aluminum-based/lead-calcium-tin-aluminum composite rods are bent to form a positive grid frame and positive symmetrical S-shaped grid ribs, and the positive grid frame and positive symmetrical S-shaped grid ribs are welded to form a grid-shaped positive plate; The specific method is: after the aluminum-based/lead-calcium-tin-aluminum composite rod is calibrated, take the calibrated point as the apex of the arc, and bend it twice according to R=25mm to form a positive grid frame, and the straight rods at both ends of the arc form a right angle; According to the calibrated length of the aluminum-based/lead-calcium-tin-aluminum composite rod with a distance of 40mm between the bending points, the calibration point is used as the arc on the two-dimensional plane to be bent according to R=20mm, and the forward and reverse are alternately bent, and the straight rods at both ends of the arc are bent The included angle is 115°, where the contact position between the bending rod and the bottom of the frame is calibrated according to the bending point spacing of 60mm, and the calibrated point is set as the apex of the arc to form an arc with a radius R=30mm;

d. Weld the positive aluminum conductive beam to the top of the grid-type positive plate, place it in methanesulfonic acid solution A, use the cast pure lead plate as the anode, and heat it at a temperature of 45°C, a current density of 2A/dm ² , and mechanical stirring Electroplate the lead-cobalt-antimony rare earth/silver-coated aluminum powder composite layer for 3 hours to obtain the positive grid; methanesulfonic acid solution A contains lead methanesulfonate (Pb(CH ₃ SO ₃ ) ₂ ) 120g/L, methanesulfonate Cobalt acid (Co(CH ₃ SO ₃ ) ₂ ) 16g/L, antimony potassium tartrate 8g/L, nano CeO ₂ 12g/L, silver-coated aluminum powder 6g/L;

e. Coating the positive lead paste on the positive grid, curing and drying to obtain the positive composite plate of the lead-carbon energy storage battery;

S2. Preparation of Negative Grid

a. Preparation of Ni-TiB ₂ composite transition layer: Alkaline washing, deionized water washing, ultrasonic cleaning, primary zinc immersion, deionized water washing, nitric acid activation, deionized water washing, secondary zinc immersion, chemical composite Ni plating -TiB ₂ , washed with deionized water, and dried to obtain a Ni-TiB ₂ composite transition layer composite rod;

The zinc dipping solution contains NaOH 300g/L, ZnO 70g/L, potassium sodium tartrate 12g/L, the zinc dipping temperature is 30°C, and the time is 60S;

The electroless composite Ni-TiB ₂ plating solution contains NiSO ₄ 7H ₂ O 70g/L, hydrazine hydrate 20g/L, sodium acetate 20g/L, nano-TiB ₂ 7g/L, the pH value of the plating solution is 10, chemical composite The temperature of Ni-TiB ₂ plating is 90°C, and the pulling speed is 5m/min;

b. Preparation of lead-calcium-aluminum interlayer: Ni-TiB ₂ composite transition layer composite rod is heat-treated at a temperature of 200°C for 7 minutes, placed in a drawing and coating extruder, and coated with semi-molten lead-calcium-aluminum alloy On the surface of the Ni-TiB ₂ composite transition layer composite rod, an aluminum-based/lead-calcium-aluminum composite rod is obtained;

c. Aluminum-based/lead-calcium-aluminum composite rods are bent to form a negative grid frame and negative symmetrical S-shaped grid ribs, and the negative grid frame and negative symmetrical S-shaped grid ribs are welded to form a grid-shaped negative plate; The method is: after the aluminum-based/lead-calcium-aluminum composite rod is calibrated in size, take the calibrated point as the apex of the arc, bend it twice according to R=25mm to form the frame of the negative grid, and the straight rods at both ends of the arc form a right angle; according to the aluminum The distance between the bending points of the base/lead-calcium-aluminum composite rod is 40mm and the calibrated length is laid on the two-dimensional plane with the calibrated point as an arc. It is bent according to R=20mm, and the forward and reverse are alternately bent. The angle between the straight rods at both ends of the arc is 115°, wherein the contact position between the bending rod and the bottom of the frame is calibrated according to the bending point spacing of 60mm, and the calibrated point is set as the arc apex with a radius R=30mm;

d. Weld the negative aluminum conductive beam to the top of the grid-type negative plate, place it in methanesulfonic acid solution B, use the cast pure lead plate as the anode, and stir it at a temperature of 45°C and a current density of 2A/dm ² . Electroplate _{the lead -} tin-antimony/zirconia composite layer for 3 hours under the condition of Tin (Sn(CH ₃ SO ₃ ) ₂ ) 20g/L, antimony potassium tartrate 5g/L, nano ZrO ₂ 12g/L, o-chlorobenzaldehyde 0.3g/L;

e. Coating the negative electrode paste on the negative electrode grid, curing and drying to obtain the negative electrode composite plate of the lead-carbon energy storage battery;

Battery assembly process: the positive and negative plates are covered with separator paper on both sides, the negative electrode is the first piece, followed by the positive electrode, alternately stacked, the electrode group has a structure of 7 positive and 8 negative, and the electrode group is clamped and pressed into the battery case ; After the battery is sealed, sealed, and airtight tested, the assembly is completed, and the performance is finally tested;

The positive and negative plates made of the composite grid of this embodiment have strong deformation resistance and creep resistance. Compared with the traditional lead-0.06% calcium-1.2% tin alloy grid, the tensile strength is increased by 90%, and the conductivity of the plate is Increased by 60%, high current discharge performance increased by 30%, and heavy metal lead consumption reduced by 60%.

Embodiment 2: The structure of the aluminum-based composite pole plate for the large-capacity and long-life lead-carbon energy storage battery in this embodiment is basically the same as that of the aluminum-based composite pole plate grid in Example 1, except that:

Aluminum-based lead-cobalt-antimony rare earth/silver-coated aluminum powder composite rod 11 includes aluminum alloy rod (1060), Ni-Sn/rare earth composite transition layer, lead-calcium-tin-aluminum intermediate layer and lead-cobalt-antimony rare earth/silver-coated Aluminum powder active layer, aluminum-based lead-tin-antimony/zirconia particle composite rod 21 sequentially includes aluminum alloy rod (1050), Ni-TiB ₂ composite transition layer, lead-calcium-aluminum intermediate layer and lead-tin-antimony/zirconia particle composite rod 21 from inside to outside. The outer layer of zirconia particles; aluminum-based lead-cobalt-antimony rare earth/silver-coated aluminum powder composite rod 11. The diameter of the rod (1060) is 2.5 mm, the thickness of the Ni-Sn/rare earth composite transition layer is 1 μm, the thickness of the lead-calcium-tin-aluminum intermediate layer is 0.5 mm, and the thickness of the lead-cobalt-antimony rare earth/silver-coated aluminum powder active layer is 0.1 mm; The cross-section of the aluminum alloy rod (1050) in lead-tin-antimony/zirconia particle composite rod 21 is a rectangular tooth shape, the depth of the tooth pattern is 0.05mm, the width of the tooth pattern is 0.05mm, and the diameter of the aluminum alloy rod (1050) is 1.5mm , the thickness of the Ni-TiB ₂ composite transition layer is 1 μm, the thickness of the lead-calcium-aluminum intermediate layer is 0.5 mm, and the thickness of the lead-tin-antimony/zirconia outer layer is 0.1 mm;

The rare earth in the Ni-Sn/rare earth composite transition layer in the aluminum-based lead-cobalt-antimony rare earth/silver-coated aluminum powder composite rod 11 is _CeO2 , and the doping amount of rare earth is 0.05wt.%. The calcium content in the lead-calcium-tin-aluminum interlayer is The content of tin is 0.04wt.%, the content of tin is 0.1wt.%, and the content of aluminum is 0.01wt.%. The rare earth in the active layer of lead cobalt antimony rare earth/silver coated aluminum powder is Nd, the content of cobalt is 0.01wt.%, and the content of antimony is 0.05 wt.%, the content of rare earth is 0.01wt.%, the content of silver-coated aluminum powder is 0.2wt.%, and the content of silver-coated aluminum powder is 5wt.%.

The _TiB2 doping amount of the Ni- _TiB2 composite transition layer in the aluminum-based lead-tin-antimony/zirconia particle composite rod 21 is 0.1wt.%, the calcium content in the lead-calcium-aluminum interlayer is 0.05wt.%, and the aluminum content is 0.01wt.%, the rest is lead; the content of tin in the outer layer of lead-tin-antimony/zirconia is 0.5wt.%, the content of antimony is 0.1wt.%, and the content of zirconia is 0.5wt.%.

The grid-type positive plate includes a positive grid frame and a positive symmetrical S-shaped grid rib, and the grid-type negative plate includes a negative grid frame and a negative symmetrical S-shaped grid rib;

The thickness of the positive aluminum alloy conductive beam is 6mm, and the thickness of the negative aluminum alloy conductive beam is 4mm. Both the positive aluminum alloy conductive beam and the negative aluminum alloy conductive beam include aluminum or aluminum alloy matrix, hard anodized Film layer, anti-corrosion PTFE composite modified primer layer and silicone metal glue anti-corrosion layer;

The thickness of the hard anodized film layer is 20 μm, the thickness of the anti-corrosion PTFE composite modified primer layer is 20 μm, and the thickness of the silicone metal glue anti-corrosion layer is 40 μm;

The preparation method of the positive plate aluminum alloy conductive beam, the specific steps are as follows:

(1) The aluminum alloy conductive beam is sequentially washed with a NaOH solution with a concentration of 10wt.% to remove oil and deionized water to obtain a pretreated aluminum alloy conductive beam;

(2) Place the pretreated aluminum alloy conductive beam in a modified sulfuric acid solution at a temperature of 0.5°C, a current density of 0.5A/dm ² , a cell voltage of 60V, and carry out hard anodic oxidation for 1 hour under the condition of blowing and stirring at the bottom. After cleaning with deionized water, place it in hot water to seal, blow dry, and then place it at a temperature of 400°C for 0.5 hours in vacuum heat treatment to obtain a hard anodized film layer; the modified sulfuric acid solution contains 200g/L of sulfuric acid, 16ml/L of glycerin, Oxalic acid 10g/L, aluminum sulfate 10g/L;

(3) Immerse the aluminum alloy conductive beam coated with the hard anodic oxidation film layer in the modified PTFE emulsion with a temperature of 60° C. and coat it for 2 minutes to obtain the anti-corrosion PTFE composite modified primer layer;

(4) At a temperature of 70°C, apply commercially available silica gel to metal glue on the surface of an aluminum alloy conductive beam coated with an anti-corrosion PTFE composite modified primer layer and cure for 1 hour to obtain a silica gel to metal glue anti-corrosion layer;

Based on the mass of positive lead paste as 100%, lead powder 75%, hollow glass microspheres/MnO ₂ 1.0%, tetrabasic lead sulfate powder 1.0%, colloidal graphite 0.1%, short fiber 0.10%, silicon dioxide 0.5% , sulfuric acid solution 6.0%, H ₂ O 9.0%; based on the mass of the negative lead paste as 100%, lead powder 75%, colloidal graphite 0.2%, modified carbon material composite powder 0.5%, superfine barium sulfate 0.3%, wood Sodium 0.1%, short fiber 0.10%, sulfuric acid solution 6.0%, H ₂ O 9%; the thickness of the positive electrode paste layer is 5mm, and the thickness of the negative electrode paste layer is 4mm;

Hollow glass microsphere/ _MnO Content of MnO in the hollow glass microsphere/MnO ₂ is 10wt.%; Described hollow glass microsphere/ _MnO The preparation method, concrete steps are as follows:

(1) The hollow glass microspheres are successively roughened with 5g/L KF solution, sensitized with 5g/L _SnC1 +5ml/L hydrochloric acid solution, and activated with 1g/L _AgNO3 solution to obtain activated hollow glass microspheres;

(2) Soak activated hollow glass microspheres in 10wt.% Mn(NO ₃ ) ₂ -dehydrated ethanol solution for 5 minutes, and then sinter at 100°C for 10 minutes; repeat soaking and sintering 4 times to obtain activated hollow glass microspheres. Glass beads/MnO ₂ ;

The modified carbon material composite powder is coconut shell activated carbon chemically plated lead-tin alloy, and the lead content in the coconut shell activated carbon chemically plated lead-tin alloy is 10wt.%, and the tin content is 10wt.%.

The preparation method of described coconut shell activated carbon electroless lead-tin alloy plating, concrete steps are as follows:

(1) Coconut shell activated carbon is roughened successively through 5g/L KF solution, 5g/L SnC1 ₂ +5ml/L hydrochloric acid solution sensitization, 0.2g/L PdC1 ₂ solution activation treatment to obtain activated coconut shell activated carbon;

(2) Activated coconut shell activated carbon is placed in the neutral chemical lead-tin alloy plating solution, and electroless plating is performed at a temperature of 60 ° C for 1 hour to obtain coconut shell activated carbon chemical lead-tin alloy plating; the neutral chemical lead-tin alloy plating solution contains PbCl ₂ 10g/L, SnCl ₂ 10g/L, EDTA 10g/L, trisodium citrate 60g/L, nitrilotriacetic acid 10g/L, TiCl ₃ (50%) 10mL/L; The pH value is 5;

The preparation method of the aluminum-based composite pole plate for the lead-carbon energy storage battery with large capacity and long life, the specific steps are as follows:

S1. Preparation of positive grid

a. Preparation of Ni-Sn/rare earth composite transition layer: the aluminum alloy rod (1060) is sequentially subjected to alkali washing, deionized water washing, ultrasonic cleaning, primary zinc immersion, deionized water washing, nitric acid activation, deionized water washing, and secondary immersion. Zinc, chemical composite Ni-Sn/rare earth plating, deionized water washing, drying automatic production line to obtain Ni-Sn/rare earth composite transition layer composite rod;

The zinc dipping solution contains NaOH 200g/L, ZnO 50g/L, potassium sodium tartrate 5g/L, the zinc dipping temperature is 20°C, and the time is 30S;

The electroless composite Ni-Sn/rare earth plating solution contains NiSO ₄ 7H ₂ O 25g/L, SnCl ₄ 5g/L, NaHPO ₂ 10g/L, sodium acetate 10g/L, glacial acetic acid 1ml/L, rare earth 1g/L, the pH value of the plating solution is 4.4, the temperature of chemical composite Ni-Sn/rare earth plating is 80°C, and the pulling speed is 2m/min;

b. Preparation of the lead-calcium-tin-aluminum intermediate layer: the Ni-Sn/rare earth composite transition layer composite rod is heat-treated at a temperature of 120°C for 5 minutes, placed in a drawing and coating extruder, and the semi-molten lead-calcium-tin-aluminum The alloy is coated on the surface of the Ni-Sn/rare earth composite transition layer composite rod to obtain an aluminum-based/lead-calcium-tin-aluminum composite rod;

c. Aluminum-based/lead-calcium-tin-aluminum composite rods are bent to form a positive grid frame and positive symmetrical S-shaped grid ribs, and the positive grid frame and positive symmetrical S-shaped grid ribs are welded to form a grid-shaped positive plate; The specific method is: after the aluminum-based/lead-calcium-tin-aluminum composite rod is calibrated in size, take the calibrated point as the apex of the arc, and bend it twice according to R=20mm to form a positive grid frame, and the straight rods at both ends of the arc form a right angle; According to the 20mm calibrated length between the bending points of the aluminum base/lead-calcium-tin-aluminum composite rod, the calibrated points are used as the arc on the two-dimensional plane to be bent according to R=8mm, and the forward and reverse are alternately bent, and the straight rods at both ends of the arc are bent. The included angle is 105°, where the contact position between the bending rod and the bottom of the frame is calibrated according to the bending point spacing of 50mm, and the calibrated point is set as the apex of the arc to form an arc with a radius of R=10mm;

d. Weld the positive aluminum alloy conductive beam to the top of the grid-type positive plate, place it in methanesulfonic acid solution A, use the cast pure lead plate as the anode, and heat it at a temperature of 30°C and a current density of 0.5A/dm ² . Under mechanical stirring, electroplate the lead-cobalt-antimony rare earth/silver-coated aluminum powder composite layer for 1 hour to obtain the positive electrode grid; methanesulfonic acid solution A contains lead methanesulfonate (Pb(CH ₃ SO ₃ ) ₂ ) 80g/L, and Cobalt sulfonate (Co(CH ₃ SO ₃ ) ₂ ) 8g/L, antimony potassium tartrate 4g/L, nano CeO ₂ 4g/L, silver-coated aluminum powder 2g/L;

e. Coating the positive lead paste on the positive grid, curing and drying to obtain the positive composite plate of the lead-carbon energy storage battery;

S2. Preparation of Negative Grid

a. Preparation of Ni-TiB ₂ composite transition layer: Alkaline washing, deionized water washing, ultrasonic cleaning, primary zinc immersion, deionized water washing, nitric acid activation, deionized water washing, secondary zinc immersion, chemical Composite plating of Ni-TiB ₂ , washing with deionized water, and drying to obtain a Ni-TiB ₂ composite transition layer composite rod;

The zinc dipping solution contains NaOH 200g/L, ZnO 50g/L, potassium sodium tartrate 5g/L, the zinc dipping temperature is 20°C, and the time is 30S;

The plating solution of chemical composite Ni-TiB ₂ contains NiSO ₄ 7H ₂ O 40g/L, hydrazine hydrate 10g/L, sodium acetate 10g/L, nano-TiB ₂ 2g/L, the pH value of the plating solution is 9, chemical composite The temperature of Ni-TiB ₂ plating is 80°C, and the pulling speed is 2m/min;

b. Preparation of lead-calcium-aluminum interlayer: Ni-TiB ₂ composite transition layer composite rod is heat-treated at a temperature of 120°C for 5 minutes, placed in a drawing and coating extruder, and coated with semi-molten lead-calcium-aluminum alloy On the surface of the Ni-TiB ₂ composite transition layer composite rod, an aluminum-based/lead-calcium-aluminum composite rod is obtained;

c. Aluminum-based/lead-calcium-aluminum composite rods are bent to form a negative grid frame and negative symmetrical S-shaped grid ribs, and the negative grid frame and negative symmetrical S-shaped grid ribs are welded to form a grid-shaped negative plate; The method is: after the aluminum-based/lead-calcium-aluminum composite rod is calibrated in size, take the calibrated point as the apex of the arc, bend it twice according to R=20mm to form a negative grid frame, and the straight rods at both ends of the arc form a right angle; according to the aluminum The distance between the bending points of the base/lead-calcium-aluminum composite rod is 20mm and the calibrated length is laid on the two-dimensional plane with the calibrated point as the arc. It is bent according to R=8mm, and the forward and reverse are alternately bent. The angle between the straight rods at both ends of the arc is 105°, wherein the contact position between the bending rod and the bottom of the frame is calibrated according to the bending point spacing of 50mm, and the calibrated point is set as the apex of the arc to form an arc with a radius of R=10mm;

d. Weld the negative aluminum alloy conductive beam to the top of the grid-type negative plate, place it in methanesulfonic acid solution B, and use the cast pure lead plate as the anode, at a temperature of 30°C and a current density of 0.5A/dm ² , Electroplate the lead-tin-antimony/zirconia composite layer under the condition of mechanical stirring for 1 h to obtain the negative electrode grid; the methanesulfonic acid solution B contains 40 g/L of lead methanesulfonate (Pb(CH ₃ SO ₃ ) ₂ ), methyl Tin sulfonate (Sn(CH ₃ SO ₃ ) ₂ ) 10g/L, antimony potassium tartrate 2g/L, nano ZrO ₂ 4g/L, o-chlorobenzaldehyde 0.1g/L;

e. Coating the negative electrode paste on the negative electrode grid, curing and drying to obtain the negative electrode composite plate of the lead-carbon energy storage battery;

Battery assembly process: the positive and negative plates are covered with separator paper on both sides, the negative electrode is the first piece, followed by the positive electrode, alternately stacked, the electrode group has a structure of 7 positive and 8 negative, and the electrode group is clamped and pressed into the battery case ; After the battery is sealed, sealed, and airtight tested, the assembly is completed, and the performance is finally tested;

The positive and negative plates made of the composite grid of this embodiment have strong deformation resistance and creep resistance. Compared with the traditional lead-0.06% calcium-1.2% tin alloy grid, the tensile strength is increased by 50%, and the conductivity of the plate is Increased by 30%, high current discharge performance increased by 10%, and heavy metal lead consumption reduced by 40%.

Example 3: The structure of the aluminum-based composite pole plate for the large-capacity and long-life lead-carbon energy storage battery in this example is basically the same as that of the aluminum-based composite pole plate grid in Example 1, except that:

Aluminum-based lead-cobalt-antimony rare earth/silver-coated aluminum powder composite rod 11 includes aluminum alloy rod (1070), Ni-Sn/rare earth composite transition layer, lead-calcium-tin-aluminum intermediate layer and lead-cobalt-antimony rare earth/silver-coated Aluminum powder active layer, aluminum-based lead-tin-antimony/zirconia particle composite rod 21 sequentially includes aluminum alloy rod (6061), Ni-TiB ₂ composite transition layer, lead-calcium-aluminum intermediate layer and lead-tin-antimony/zirconia particle composite rod 21 from inside to outside. The outer layer of zirconia particles; aluminum-based lead-cobalt-antimony rare earth/silver-coated aluminum powder composite rod 11. The diameter of the rod (1070) is 6.0 mm, the thickness of the Ni-Sn/rare earth composite transition layer is 10 μm, the thickness of the lead-calcium-tin-aluminum intermediate layer is 6.0 mm, and the thickness of the lead-cobalt-antimony rare earth/silver-coated aluminum powder active layer is 1.0 mm; The cross-section of the aluminum alloy rod (6061) in lead-tin-antimony/zirconia particle composite rod 21 is a rectangular tooth shape, the depth of the tooth pattern is 0.2mm, the width of the tooth pattern is 0.2mm, and the diameter of the aluminum alloy rod (6061) is 4.0mm , the thickness of the Ni-TiB ₂ composite transition layer is 10 μm, the thickness of the lead-calcium-aluminum middle layer is 4.0 mm, and the thickness of the lead-tin-antimony/zirconia outer layer is 0.5 mm;

The rare earth in the Ni-Sn/rare earth composite transition layer in the aluminum-based lead-cobalt-antimony rare earth/silver-coated aluminum powder composite rod 11 is Nd ₂ O ₃ , and the doping amount of rare earth is 0.5wt.%. In the lead-calcium-tin-aluminum intermediate layer The content of calcium is 0.1wt.%, the content of tin is 0.6wt.%, and the content of aluminum is 0.05wt.%. The rare earth in the active layer of lead-cobalt-antimony rare earth/silver-coated aluminum powder is La, the content of cobalt is 0.2wt.%, and the content of antimony 0.5wt.%, the rare earth content is 0.2wt.%, the silver-coated aluminum powder content is 2.0wt.%, and the silver-coated aluminum powder silver content is 25wt.%.

The _TiB2 doping amount of the Ni- _TiB2 composite transition layer in the aluminum-based lead-tin-antimony/zirconia particle composite rod 21 is 1.0wt.%, the calcium content in the lead-calcium-aluminum interlayer is 0.12wt.%, and the aluminum content is The content of tin in the outer layer of lead-tin-antimony/zirconia is 2.0wt.%, the content of antimony is 1wt.%, and the content of zirconium dioxide is 5wt.%.

The grid-type positive plate includes a positive grid frame and a positive symmetrical S-shaped grid rib, and the grid-type negative plate includes a negative grid frame and a negative symmetrical S-shaped grid rib;

The thickness of the positive aluminum alloy conductive beam is 20mm, and the thickness of the negative aluminum alloy conductive beam is 18mm. Both the positive aluminum alloy conductive beam and the negative aluminum alloy conductive beam include aluminum or aluminum alloy matrix, hard anodized Film layer, anti-corrosion PTFE composite modified primer layer and silicone metal glue anti-corrosion layer;

The thickness of the hard anodized film layer is 50 μm, the thickness of the anti-corrosion PTFE composite modified primer layer is 100 μm, and the thickness of the silicone metal glue anti-corrosion layer is 100 μm;

The preparation method of the positive plate aluminum alloy conductive beam, the specific steps are as follows:

(1) The aluminum alloy conductive beam is sequentially washed with a NaOH solution with a concentration of 20wt.% to remove oil and deionized water to obtain a pretreated aluminum alloy conductive beam;

(2) Place the pretreated aluminum alloy conductive beam in a modified sulfuric acid solution at a temperature of 5°C, a current density of 4A/dm ² , a cell voltage of 50V, and carry out hard anodic oxidation for 4 hours under the condition of blowing and stirring at the bottom. After cleaning with ionized water, place it in hot water to seal, blow dry, and then place it under vacuum heat treatment at 600°C for 2 hours to obtain a hard anodized film layer; the modified sulfuric acid solution contains 300g/L of sulfuric acid, 30ml/L of glycerin, and 30g of oxalic acid /L, aluminum sulfate 30g/L;

(3) Immerse the aluminum alloy conductive beam coated with the hard anodized film layer in the modified PTFE emulsion with a temperature of 120° C. and coat it for 10 minutes to obtain the anti-corrosion PTFE composite modified primer layer;

(4) At a temperature of 120°C, apply commercially available silica gel to metal glue on the surface of an aluminum alloy conductive beam coated with an anti-corrosion PTFE composite modified primer layer and cure for 3 hours to obtain a silica gel to metal glue anti-corrosion layer;

Based on the mass of positive lead paste as 100%, lead powder 90%, hollow glass microspheres/MnO ₂ 4.0%, tetrabasic lead sulfate powder 2.0%, colloidal graphite 0.8%, short fiber 0.20%, silicon dioxide 1.5% , sulfuric acid solution 11.5%, H ₂ O 13.0%; based on the mass of negative electrode paste as 100%, lead powder 85%, colloidal graphite 1.0%, modified carbon material composite powder 5.0%, ultrafine barium sulfate 1.0%, 0.5% lignin, 0.20% short fiber, 9.0% sulfuric acid solution, 14% _H2O ; the thickness of the positive electrode paste layer is 9mm, and the thickness of the negative electrode paste layer is 7mm;

Hollow glass microsphere/ _MnO Content of _MnO in the hollow glass microsphere/MnO2 is 20wt.%; Described hollow glass microsphere/ _{MnOPreparation} method, concrete steps are as follows:

(1) The hollow glass microspheres are sequentially subjected to 20g/L KF roughening solution, 20g/L SnC1 ₂ +10ml/L hydrochloric acid solution sensitization, and 5g/L AgNO ₃ solution activation treatment to obtain activated hollow glass microspheres;

(2) Activated hollow glass microspheres were soaked in 30wt.% Mn(NO ₃ ) ₂ -dehydrated ethanol solution for 20 minutes, and then sintered at 400°C for 30 minutes; repeated soaking and sintering 8 times to obtain active Hollow glass microspheres/MnO ₂ ;

The modified carbon material composite powder is coconut shell activated carbon chemically plated lead-tin alloy, and the lead content in the coconut shell activated carbon chemically plated lead-tin alloy is 10wt.%, and the tin content is 10wt.%.

The preparation method of described coconut shell activated carbon electroless lead-tin alloy plating, concrete steps are as follows:

(1) Coconut shell activated carbon is roughened successively through 20g/L KF solution, 20g/L SnCl ₂ +10ml/L hydrochloric acid solution sensitization, 1.0g/L PdCl ₂ solution activation treatment to obtain activated coconut shell activated carbon;

(2) Activated coconut shell activated carbon is placed in neutral electroless lead-tin alloy plating solution, and electroless plated at a temperature of 80 ° C for 3 hours to obtain coconut shell activated carbon electroless lead-tin alloy plating; the neutral chemical lead-tin alloy plating solution contains PbC1 ₂ 30g/L, SnC1 ₂ 30g/L, EDTA 40g/L, trisodium citrate 100g/L, nitrilotriacetic acid 40g/L, TiC1 ₃ (50%) 40mL/L; The pH value is 8;

The preparation method of the aluminum-based composite pole plate for the lead-carbon energy storage battery with large capacity and long life, the specific steps are as follows:

S1. Preparation of positive grid

a. Preparation of Ni-Sn/rare earth composite transition layer: the aluminum alloy rod (1070) is sequentially washed with alkali, deionized water, ultrasonic cleaning, primary zinc dipping, deionized water washing, nitric acid activation, deionized water washing, and secondary immersion. Zinc, chemical composite Ni-Sn/rare earth plating, deionized water washing, drying automatic production line to obtain Ni-Sn/rare earth composite transition layer composite rod;

The zinc dipping solution contains NaOH 400g/L, ZnO 100g/L, potassium sodium tartrate 20g/L, the zinc dipping temperature is 40°C, and the time is 100S;

The electroless composite Ni-Sn/rare earth plating solution contains NiSO ₄ 7H ₂ O 45g/L, SnCl ₄ 15g/L, NaHPO ₂ 30g/L, sodium acetate 30g/L, glacial acetic acid 10ml/L, rare earth 10g/L, the pH value of the plating solution is 5.0, the temperature of chemical composite Ni-Sn/rare earth plating is 95°C, and the pulling speed is 8m/min;

b. Preparation of the lead-calcium-tin-aluminum intermediate layer: the Ni-Sn/rare earth composite transition layer composite rod is heat-treated at a temperature of 300°C for 10 minutes, placed in a drawing and coating extruder, and the semi-molten lead-calcium-tin-aluminum The alloy is coated on the surface of the Ni-Sn/rare earth composite transition layer composite rod to obtain an aluminum-based/lead-calcium-tin-aluminum composite rod;

c. Aluminum-based/lead-calcium-tin-aluminum composite rods are bent to form a positive grid frame and positive symmetrical S-shaped grid ribs, and the positive grid frame and positive symmetrical S-shaped grid ribs are welded to form a grid-shaped positive plate; The specific method is: after the aluminum-based/lead-calcium-tin-aluminum composite rod is calibrated in size, take the calibrated point as the apex of the arc, and bend it twice according to R=30mm to form a positive grid frame, and the straight rods at both ends of the arc form a right angle; According to the calibrated length of the aluminum-based/lead-calcium-tin-aluminum composite rod bending point spacing of 60mm, the calibration point is used as the arc on the two-dimensional plane to be bent according to R=30mm, and the forward and reverse are alternately bent, and the straight rods at both ends of the arc are bent. The included angle is 130°, where the contact position between the bending rod and the bottom of the frame is calibrated according to the bending point spacing of 80mm, and the calibrated point is set as the apex of the arc to form an arc with a radius R=40mm;

d. Weld the positive aluminum alloy conductive beam to the top of the grid-type positive plate, place it in methanesulfonic acid solution A, use the cast pure lead plate as the anode, and heat it at a temperature of 60°C and a current density of 4.0A/dm ² . Under mechanical stirring, the composite layer of lead cobalt antimony rare earth/silver-coated aluminum powder was electroplated for 6 hours to obtain a positive electrode grid; methanesulfonic acid solution A contained lead methanesulfonate (Pb(CH ₃ SO ₃ ) ₂ ) 200g/L, form Cobalt sulfonate (Co(CH ₃ SO ₃ ) ₂ ) 24g/L, antimony potassium tartrate 12g/L, nano CeO ₂ 20g/L, silver-coated aluminum powder 10g/L;

e. Coating the positive lead paste on the positive grid, curing and drying to obtain the positive composite plate of the lead-carbon energy storage battery;

S2. Preparation of Negative Grid

a. Preparation of Ni-TiB ₂ composite transition layer: Alkaline washing, deionized water washing, ultrasonic cleaning, primary zinc immersion, deionized water washing, nitric acid activation, deionized water washing, secondary zinc immersion, chemical Composite plating of Ni-TiB ₂ , washing with deionized water, and drying to obtain a Ni-TiB ₂ composite transition layer composite rod;

The zinc dipping solution contains NaOH 400g/L, ZnO 100g/L, potassium sodium tartrate 20g/L, the zinc dipping temperature is 40°C, and the time is 100S;

The electroless composite Ni-TiB ₂ plating solution contains NiSO ₄ 7H ₂ O 100g/L, hydrazine hydrate 30g/L, sodium acetate 30g/L, nano-TiB ₂ 12g/L, the pH value of the plating solution is 10, chemical composite The temperature of Ni-TiB ₂ plating is 95°C, and the pulling speed is 8m/min;

b. Preparation of the lead-calcium-aluminum intermediate layer: heat-treat the Ni-TiB ₂ composite transition layer composite rod at a temperature of 300°C for 10 minutes, place it in a drawing and coating extruder, and coat it with semi-molten lead-calcium-aluminum alloy On the surface of the Ni-TiB ₂ composite transition layer composite rod, an aluminum-based/lead-calcium-aluminum composite rod is obtained;

c. Aluminum-based/lead-calcium-aluminum composite rods are bent to form a negative grid frame and negative symmetrical S-shaped grid ribs, and the negative grid frame and negative symmetrical S-shaped grid ribs are welded to form a grid-shaped negative plate; The method is: after the aluminum-based/lead-calcium-aluminum composite rod is calibrated in size, take the calibrated point as the apex of the arc, bend it twice according to R=30mm to form the frame of the negative grid, and the straight rods at both ends of the arc form a right angle; according to the aluminum The distance between the bending points of the base/lead-calcium-aluminum composite rod is 60mm and the calibrated length is laid on the two-dimensional plane with the calibrated point as the arc. It is bent according to R=30mm, and the forward and reverse are alternately bent. The angle between the straight rods at both ends of the arc is 130°, wherein the contact position between the bending rod and the bottom of the frame is calibrated according to the bending point spacing of 80mm, and the calibrated point is set as the apex of the arc to form an arc of radius R=40mm;

d. Weld the negative aluminum alloy conductive beam to the top of the grid-shaped negative plate, place it in methanesulfonic acid solution B, and use the cast pure lead plate as the anode, at a temperature of 60°C and a current density of 4.0A/dm ² , Electroplate the lead-tin-antimony/zirconia composite layer under the condition of mechanical stirring for 6 hours to obtain the negative electrode grid; methanesulfonic acid solution B contains lead methanesulfonate (Pb(CH ₃ SO ₃ ) ₂ ) 120g/L, methyl Tin sulfonate (Sn(CH ₃ SO ₃ ) ₂ ) 30g/L, antimony potassium tartrate 8g/L, nanometer ZrO ₂ 20g/L, o-chlorobenzaldehyde 0.5g/L;

e. Coating the negative electrode paste on the negative electrode grid, curing and drying to obtain the negative electrode composite plate of the lead-carbon energy storage battery;

Battery assembly process: the positive and negative plates are covered with separator paper on both sides, the negative electrode is the first piece, followed by the positive electrode, alternately stacked, the electrode group has a structure of 7 positive and 8 negative, and the electrode group is clamped and pressed into the battery case ; After the battery is sealed, sealed, and airtight tested, the assembly is completed, and the performance is finally tested;

The positive and negative plates made of the composite grid of this embodiment have strong resistance to deformation and creep. Compared with the traditional lead-0.06% calcium-1.2% tin alloy grid, the tensile strength is increased by 60%, and the conductivity of the plate is Increased by 35%, high current discharge performance increased by 20%, and the amount of heavy metal lead reduced by 45%.

The specific implementation of the present invention has been described in detail above, but the present invention is not limited to the above-mentioned implementation, within the knowledge of those of ordinary skill in the art, various modifications can be made without departing from the spirit of the present invention. Variety.

Claims (10)

1. A large-capacity and long-life aluminum-based composite pole plate for lead-carbon energy storage batteries, characterized in that: it includes alternately arranged positive composite pole plates for lead-carbon energy storage batteries and negative composite pole plates for lead-carbon energy storage batteries. The positive composite pole plate of the energy storage battery includes a positive pole grid (1) and a positive electrode paste coated on the positive pole grid (1), and the negative composite pole plate of the lead-carbon energy storage battery includes a negative pole grid (2) and a coating Negative electrode lead paste arranged on the negative electrode grid (2); The positive grid (1) includes a grid-type positive plate and a positive plate aluminum conductive beam (12) arranged on the top of the grid-type positive plate, and the negative grid (2) includes a grid-type negative plate and a positive plate aluminum conductive beam (12) arranged on the top of the grid-type positive plate. The negative plate aluminum conductive beam (22) at the top of the plate; the grid-type positive plate is composed of aluminum-based lead-cobalt-antimony rare earth/silver-coated aluminum powder composite rod (11), and the grid-type negative plate is composed of aluminum-based lead-tin-antimony/ Composition of zirconia particle composite rod (21); The top of the positive plate aluminum conductive beam (12) is fixedly provided with a positive tab (13), and the top of the negative aluminum conductive beam is fixedly provided with a negative tab (23). 23) Connected through the negative confluence L-shaped aluminum bar, the ends of the positive confluence L-shaped aluminum bar and the negative confluence L-shaped aluminum bar are equipped with copper-aluminum composite conductive heads for external power lines. The aluminum-based lead-cobalt-antimony rare earth/silver-coated aluminum powder composite rod (11) sequentially includes an aluminum or aluminum alloy rod, a Ni-Sn/rare earth composite transition layer, a lead-calcium-tin-aluminum intermediate layer and a lead-cobalt-antimony rare earth /Silver-coated aluminum powder active layer, aluminum-based lead-tin-antimony/zirconia particle composite rod (21) sequentially includes aluminum or aluminum alloy rod, Ni-TiB ₂ composite transition layer, lead-calcium-aluminum intermediate layer and lead Tin antimony/zirconia grain outer layer. 2. According to claim 1, the aluminum-based composite polar plate for large-capacity and long-life lead-carbon energy storage batteries is characterized in that: aluminum or aluminum alloy rods in aluminum-based lead-cobalt-antimony rare earth/silver-coated aluminum powder composite rods (11) The cross-section is a rectangular tooth shape, the depth of the tooth pattern is 0.1-0.3mm, the tooth pattern width is 0.05-0.3mm, the diameter of the aluminum or aluminum alloy rod is 0.5-6.0mm, and the thickness of the Ni-Sn/rare earth composite transition layer is 1-10μm , the thickness of the lead-calcium-tin-aluminum intermediate layer is 0.5-6.0mm, the thickness of the lead-cobalt-antimony rare earth/silver-coated aluminum powder active layer is 0.1-1.0mm; the aluminum-based lead-tin-antimony/zirconia particle composite rod (21) Or the cross-section of the aluminum alloy rod is a rectangular tooth shape, the depth of the tooth pattern is 0.05-0.2mm, the width of the tooth pattern is 0.05-0.2mm, the diameter of the aluminum or aluminum alloy rod is 0.5-4.0mm, and the thickness of the Ni-TiB ₂ composite transition layer is 1-10 μm, the thickness of the lead-calcium-aluminum middle layer is 0.5-4.0 mm, and the thickness of the lead-tin-antimony/zirconia outer layer is 0.1-0.5 mm. 3. According to claim 1, the aluminum-based composite polar plate for large-capacity and long-life lead-carbon energy storage batteries is characterized in that: Ni-Sn/rare earth in the aluminum-based lead-cobalt-antimony rare earth/silver-coated aluminum powder composite rod (11) The rare earth in the composite transition layer is CeO ₂ , La ₂ O ₃ or Nd ₂ O ₃ , and the rare earth doping amount is 0.05-0.5wt.%. The calcium content in the lead-calcium-tin-aluminum interlayer is 0.04-0.1wt.%. 0.1-0.6wt.%, the aluminum content is 0.01-0.05wt.%; the rare earth in the lead-cobalt-antimony rare earth/silver-coated aluminum powder active layer is Ce, Nd, Pr or La, and the cobalt content is 0.01-0.2wt.%, The content of antimony is 0.05-0.5wt.%, the content of rare earth is 0.01-0.2wt.%, the content of silver-coated aluminum powder is 0.2-2wt.%, and the content of silver-coated aluminum powder is 5-25wt.%. The _TiB2 doping amount of the Ni- _TiB2 composite transition layer in the aluminum-based lead-tin-antimony/zirconia particle composite rod (21) is 0.1-1wt.%, and the calcium content in the lead-calcium-aluminum intermediate layer is 0.05-0.12wt. %, the content of aluminum is 0.01-0.1wt.%, and the rest is lead; 0.5～5wt.%. 4. According to claim 1, the aluminum-based composite plate for large-capacity and long-life lead-carbon energy storage battery is characterized in that: the grid-type positive plate includes a positive grid frame and a positive symmetrical S-shaped grid rib, and the grid The negative plate includes a negative grid frame and negative symmetrical S-shaped grid ribs. 5. According to claim 1, the aluminum-based composite polar plate for large-capacity and long-life lead-carbon energy storage battery is characterized in that: the aluminum conductive beam (12) of the positive plate and the aluminum conductive beam (22) of the negative plate are all from the inside to the outside In turn, it includes an aluminum or aluminum alloy substrate, a hard anodized film layer, an anti-corrosion PTFE composite modified primer layer, and a silica gel-bonded metal glue anti-corrosion layer. 6. According to claim 5, the aluminum-based composite pole plate for large-capacity and long-life lead-carbon energy storage batteries is characterized in that: the thickness of the hard anodized film layer is 20-50 μm, and the thickness of the anti-corrosion PTFE composite modified primer layer is 20-100 μm, and the thickness of the silicone-metal glue anti-corrosion layer is 40-200 μm. 7. According to claim 1, the aluminum-based composite pole plate for large-capacity and long-life lead-carbon energy storage battery is characterized in that: based on the mass of positive electrode paste as 100%, 75-90% of lead powder, hollow glass microspheres /MnO ₂ 1.0～4.0%, tetrabasic lead sulfate powder 1.0～2.0%, colloidal graphite 0.1～0.8%, short fiber 0.1～0.2%, silicon dioxide 0.5～1.5%, sulfuric acid solution 6.0～11.5%, H ₂ O 9.0-13.0%; based on the mass of negative electrode paste as 100%, lead powder 75-85%, colloidal graphite 0.2-1.0%, modified carbon material composite powder 0.5-5.0%, ultra-fine barium sulfate 0.3-1.0% , lignin 0.1~0.5%, short fiber 0.1~0.2%, sulfuric acid solution 6.0~9.0%, H ₂ O 9~14%; the thickness of the positive electrode paste layer is 5~9mm, and the thickness of the negative electrode paste layer is 4~ 7mm. 8. According to claim 7, the aluminum-based composite pole plate for large-capacity and long-life lead-carbon energy storage battery is characterized in that: the content of _MnO in the hollow glass microsphere/ _MnO is 10-20wt.%; The modified carbon material composite powder is the coconut shell activated carbon chemically plated lead-tin alloy, and the lead content in the coconut shell activated carbon chemically plated lead-tin alloy is 10-20wt.%, and the tin content is 10-20wt.%. 9. The method for preparing an aluminum-based composite pole plate for a lead-carbon energy storage battery with large capacity and long life according to any one of claims 1 to 8, wherein the specific steps are as follows: S1. Preparation of positive grid a. Preparation of Ni-Sn/rare earth composite transition layer: Alkaline washing, deionized water washing, ultrasonic cleaning, primary zinc immersion, deionized water washing, nitric acid activation, deionized water washing, secondary zinc immersion, Electroless composite Ni-Sn/rare earth plating, deionized water washing, drying to obtain Ni-Sn/rare earth composite transition layer composite rod; b. Preparation of the lead-calcium-tin-aluminum intermediate layer: the Ni-Sn/rare earth composite transition layer composite rod is heat-treated at a temperature of 120-300 °C for 5-10 minutes, placed in a drawing and coating extruder, and the semi-molten state Lead-calcium-tin-aluminum alloy is coated on the surface of the Ni-Sn/rare earth composite transition layer composite rod to obtain an aluminum-based/lead-calcium-tin-aluminum composite rod; c. Aluminum-based/lead-calcium-tin-aluminum composite rods are bent to form a positive grid frame and positive symmetrical S-shaped grid ribs, and the positive grid frame and positive symmetrical S-shaped grid ribs are welded to form a grid-shaped positive plate; d. Weld the positive aluminum conductive beam to the top of the grid-type positive plate, and place it in methanesulfonic acid solution A to electroplate the lead-cobalt-antimony rare earth/silver-coated aluminum powder composite layer to obtain the positive grid; e. Coating the positive lead paste on the positive grid, curing and drying to obtain the positive composite plate of the lead-carbon energy storage battery; S2. Preparation of Negative Grid a. Preparation of Ni-TiB ₂ composite transition layer: Alkaline washing, deionized water washing, ultrasonic cleaning, primary zinc immersion, deionized water washing, nitric acid activation, deionized water washing, secondary zinc immersion, chemical Composite plating of Ni-TiB ₂ , washing with deionized water, and drying to obtain a Ni-TiB ₂ composite transition layer composite rod; b. Preparation of the lead-calcium-aluminum intermediate layer: heat-treat the Ni-TiB ₂ composite transition layer composite rod at a temperature of 120-300°C for 5-10 minutes, place it in a drawing and coating extruder, and put the semi-molten lead-calcium Aluminum alloy is coated on the surface of the Ni-TiB ₂ composite transition layer composite rod to obtain an aluminum-based/lead-calcium-aluminum composite rod; c. Aluminum-based/lead-calcium-aluminum composite rods are bent to form a negative grid frame and negative symmetrical S-shaped grid ribs, and the negative grid frame and negative symmetrical S-shaped grid ribs are welded to form a grid-shaped negative plate; d. Weld the negative aluminum conductive beam to the top of the grid-type negative plate, and place it in methanesulfonic acid solution B to electroplate the lead-tin-antimony/zirconia composite layer to obtain the negative grid; e. Coating the negative electrode lead paste on the negative electrode grid, curing and drying to obtain the negative electrode composite plate of the lead-carbon energy storage battery. 10. according to the preparation method of the described large-capacity long-life lead-carbon energy storage battery aluminum-based composite plate of claim 9, it is characterized in that: The zinc dipping solution contains NaOH 200~400g/L, ZnO 50~100g/L, potassium sodium tartrate 5~20g/L, the zinc dipping temperature is 20~40°C, and the time is 30~100S; The electroless composite Ni-Sn/rare earth plating solution contains NiSO ₄ 7H ₂ O 25～45g/L, SnC1 ₄ 5～15g/L, NaHPO ₂ 10～30g/L, sodium acetate 10～30g/L, ice Acetic acid 1-10ml/L, rare earth 1-10g/L, bath pH 4.4-5.0, chemical composite Ni-Sn/rare earth plating temperature 80-95°C, traction speed 2-8m/min; Methanesulfonic acid solution A contains 80-200g/L of lead methanesulfonate, 8-24g/L of cobalt methanesulfonate, 4-12g/L of antimony potassium tartrate, 4-20g/L of nano-CeO ₂ , and silver-coated Aluminum powder 2-10g/L; the anode of the electroplated lead-cobalt-antimony rare earth/silver-coated aluminum powder composite layer is cast pure lead plate, the temperature is 30-60°C, the current density is 0.5-4A/dm ² , and the time is 1-6h ; The electroless composite Ni-TiB ₂ plating solution contains NiSO ₄ 7H ₂ O 40-100g/L, hydrazine hydrate 10-30g/L, sodium acetate 10-30g/L, nano-TiB ₂ 2-12g/L, The pH value of the solution is 9~10, the temperature of chemical composite Ni-TiB ₂ plating is 80~95℃, and the pulling speed is 2~8m/min; Methanesulfonic acid solution B contains 40-120g/L lead methanesulfonate, 10-30g/L stannous methanesulfonate, 2-8g/L antimony potassium tartrate, 4-20g/L nanometer _ZrO2 , and Chlorobenzaldehyde 0.1～0.5g/L; the anode of electroplating lead-tin-antimony/zirconia composite layer is cast pure lead plate, the temperature is 30～60℃, the current density is 0.5～4A/dm ² , and the time is 1～6h .